Photovoltaics manufactured using organic materials as a substitute for inorganic materials may provide for cheaper production of solar cells if their efficiencies can be made comparable to existing technologies. Photovoltaic devices are comprised of layered structures where the electrical, chemical, and physical properties at the multiple interfaces play a significant role in the operation of the completed device. This thesis attempts to establish a relationship between interfacial properties and overall device performance by investigation of both the organic/organic heterojunction interface, as well as the interface between the inorganic substrate and the first organic layer with useful insights towards enhancing the efficiency of organic solar cells.It has been proposed that residual chemical species may act as barriers to charge transfer at the interface between the transparent conductor (TCO) and the first organic layer, possibly causing a large contact resistance and leading to reduced device performance. Previous work has investigated the surface of the TCO but no baseline characterization of carbon-free surfaces has previously been given. In this work clean surfaces are investigated to develop a fundamental understanding of the intrinsic spectra such that further analyses of contaminated surfaces can be presented systematically and reproducibly to develop a chemical model of the TCO surface.The energy level offset at the organic/organic heterojunction has been proposed to relate to the maximum potential achievable for a solar cell under illumination, however, few experimental observations have been made where both the interface characterization and device performance are presented. Photovoltaic properties are examined in this work with titanyl phthalocyanine used as a novel donor material for enhancement of spectral absorption and optimization of the open-circuit potential. Characterization of the interface between TiOPc and C60 coupled with characterization of the interface between copper phthalocyanine and C60 shows that the higher ionization potential of TiOPc does correlate to greater open circuit potentials.Examination of photovoltaic behavior using equivalent circuit modeling relates the importance of series resistance and recombination to the homogeneity of the solar cell structure.

The design of nonlinear optical (NLO) molecules has become a focus of current research in telecommunications, information technologies and optical data storage. Donor-acceptor substituted dipolar molecules have been the most investigated NLO chromophores. Dipolar molecules, however, have several limitations such as low optical transparency, low thermal stability and their strong tendency to adopt anti-parallel packing in the solid state. Recently, a new class of materials based on octupolar symmetries, which lack permanent dipole moments, has been proposed for NLO applications. At a structural level, it can be shown that the basic template for 3D octupolar molecules comes to a cube with alternating charges at the corners such as donor and acceptor substituent. Despite all the various structures reported, it is worth noting that no molecules actually representing the "real" octupolar cube have been obtained so far. In this thesis, we showed that the real octupolar cube can be demonstrated by lanthanide III complexes based on ABAB type phthalocyanine featuring alternating electron donor and electron acceptor groups. These structures are characterized by UV-NIR, X-Ray and exhibit highest quadratic hyperpolarizability ever reported for an octupolar molecule. Moreover, this work was extended to nonoctupolar lanthanide homoleptic double-decker complexes based on AB3, A4, B4, T4 type phthalocyanines. It was observed that these molecules present a quite large quadratic hyperpolarizability too, but smaller than the one obtained for the Ln(ABAB)2 series, as expected.

The synthetic approach was developed for the preparation of N-bridged diiron phthalocyanines substituted by different electron-withdrawing alkylsulfonyl substituents. Six novel phthalocyanines bearing small (methylsulfonyl, ethylsulfonyl and hexylsulfonyl) and bulky (t-butylsulfonyl, adamantylsulfonyl and cyclohexylsulfonyl) substituents have been prepared and characterized by electrospray ionization mass spectrometry (ESI-MS), UV-Vis, FT-IR and EPR. Two complexes (with hexylsulfonyl and t-butylsulfonyl substituents) were characterized in addition by Mössbauer techniques, X-ray photoelectron spectroscopy (XPS) and Fe K-edge X-ray absorption spectroscopy (XANES, EXAFS, high resolution Kβ emission spectroscopy). It has been evidenced that the electronic state of iron in these complexes depends on the size of the substituents. While N-bridged diiron phthalocyanines having methylsulfonyl, ethylsulfonyl and hexylsulfonyl substituents are cationic (PcFeIVNFeIVPc)+N3- complexes, N-bridged diiron phthalocyanines with bulkier t-butylsulfonyl, adamantylsulfonyl and cyclohexylsulfonyl substituents are formally neutral PcFeIIINFeIVPc species. The catalytic properties of six N-bridged diiron phthalocyanines have been studied, using tert-butyl hydroperoxide (tBuOOH) as the oxidant in the oxidation of toluene, p-xylene as well as in the oxidation of various alcohols. This thesis demonstrates the efficiency of N-bridged diiron phthalocyanines substituted by electron-withdrawing alkylsulfonyl groups as oxidation catalysts, in conditions required by environmental and industrial preoccupations

The purpose of the research work, presented in this thesis is to offer a detailed atomic level study of interfaces created by adsorption of organic molecules on metals and metal oxides to point out significant impact of substrate, dye structure as well as different mediators on the charge transfer at these interfaces, which is proven to influence the device performance to a great extent. Adsorption of organic photosensitive molecules on metals and metal-oxides is the main focus of this thesis. Phthalocyanines which are organic semiconductors offer a broad range of properties, such as thermal and chemical stability, high charge mobility and strong absorption coefficient in the visible and near-IR regions, which make them very attractive to be applied in various systems and devices. Fuel cells, organic field-effect transistors (OFETs), organic light emitting diodes (OLEDs) and solar cells are examples of phthalocyanine’s applications. The main focus of this work is to characterize the interfaces of Dye Sensitized Solar Cells (DSSCs). DSSC was invented by Michael Grätzel and Brian O’Regan in 1988. At the heart of this cell there is an oxide which is coated by a photosensitive dye. Under illumination, an electron is excited from HOMO to LUMO of the molecule, which can be further transferred to the conduction band of the oxide by a proper energy level alignment. The original state of the dye is regenerated by electron donation via the electrolyte, which usually is an organic solvent containing a redox couple e.g., iodide/triiodide. The iodide is regenerated by reduction of triiodide at the counter electrode. To improve the functionality of the cell, different additives can be added to the electrolyte. To mimic the interfaces of this cell, molecular layers of MPc (M: Fe, Zn, Mg) are adsorbed on both metallic surfaces, Au(111) and Pt(111), and rutile TiO2(110). Layers of iodine were inserted between metallic substrates and dyes to investigate the electronic properties and charge transfer at these multi-interface systems. 4-tert-butyl pyridine is a significant additive to the electrolyte and has proven to enhance the cell’s performance. This molecule was also adsorbed on Pt(111) and TiO2(110). Phthalocyanines were deposited by organic molecular beam deposition and 4TBP was evaporated at room temperature. Surface structures and reconstructions were confirmed by LEED measurements. Surface sensitive synchrotron radiation based spectroscopy methods, XPS and NEXAFS were applied to characterize these surfaces and interfaces. STM images directly give a topographical and electronic map over the surface. All measurements were carried out in UHV condition. When MPc was adsorbed on Au(111) and TiO2(110), charge transfer from molecule to substrate is suggested, while the opposite holds for MPc adsorbed on Pt(111). Moreover, stronger interaction between MPc and Pt(111) and TiO2(110) compared to Au(111) also demonstrates the effect of substrate on the charge transfer at the interface. The stronger interaction observed for these two substrates disturbed the smooth growth of a monolayer; it also resulted in bending of the molecular plane. Interaction of MPc with metallic surfaces was modified by inserting iodine at the interface. Another substrate-related effect was observed when MgPc was adsorbed on TiO2(110);  and -cross linked surfaces, where the surface reconstruction directly affect the molecular configuration as well as electronic structure at the interface. Besides, it is shown that the d-orbital filling of the central metal atom in MPc plays an important role for the properties of the molecular layer as well as charge transfer at the interface. Upon adsorption of 4TBP on Pt(111), C-H bond is dissociatively broken and molecules is adsorbed with N atoms down. Modification of surface by iodine, prevent this dissociation. In the low coverage of iodine, there is a competition between 4TBP and iodine to directly bind to Pt(111). Investigation on the adsorption of 4TBP on TiO2(110) illustrated that these molecules in low coverage regime, prefer the oxygen vacancy sites and their adsorption on these sites, results in a downward band bending at the substrate’s surface. / <p>QC 20131203</p>

Vertically aligned nanowire arrays of copper phthalocyanine (CuPc) and CuPc-Al Schottky diodes, of controllable diameter and length were fabricated by cathodic electrodeposition of CuPc into anodized alumina (AAO) templates, followed by annealing at 300 ºC in Argon. AAO over Aluminum tape and that over ITO-glass were both used as starting templates for the device fabrication. Depending on the dimensions of the starting AAO template, diameters of CuPc nanowires ranged from 30 nm to 40 nm and the lengths ranged from 500 nm to 1 μm. The temperature dependence of the phase and the absorption spectrum of the nanowires are reported. The electrodeposited nanowires (as prepared) had the preferred crystallite orientation of the α-phase. ITO formed the ohmic contact and Schottky contacts were formed between CuPc and aluminum. Insertion of a thin layer of PEDOT:PSS between CuPc nanowires and the ITO electrode improved the contact and reduced the series resistance by an order of magnitude. Schottky diodes were characterized and analyzed at room temperature and at cryogenic temperatures.

SYNTHESIS, CHARACTERIZATION, AND ELECTRICAL PROPERTIES OF DIAZOPHENYLENE AND DIAZODIPHENYLENE BRIDGED Co, Ni, Cu, Ce, AND Er PHTHALOCYANINE POLYMERS Alkan, Cemil M. Sc., Department of Polymer Science and Technology Supervisor: Prof.Dr. Leyla Aras Co- Supervisor: Prof.Dr. G&uuml / ng&ouml / r G&uuml / nd&uuml / z September 2004, 112 pages In this research, diazophenylene and diazodiphenylene bridged metal-phthalocyanine polymers were produced from diazonium salt of diaminophenylene/bensidin and pre-synthesized tetraamino metal phthalocyanines. Tetraamino metal phthalocyanine complexes of Co, Ni, Cu, Ce, and Er were obtained by reducing tetranitro metal phthalocyanine complexes synthesized from 3-nitrophthalic anhydride, urea, metal salt, and ammonium molybdate catalyst. Complexes and polymers were characterized by Fourier Transform Infrared Radiation (FTIR) and UV-Visible spectroscopies. X-Ray analysis showed that there were short range orientations in the polymers. Thermal analysis of the complexes and the polymers were done by differential scanning calorimetry and thermal gravimetric analysis at a heating rate of 10&amp / #61616 / Cmin&amp / #61485 / 1 under nitrogen atmosphere. Ash analysis was performed to determine the metal content of the polymers. Viscosity and ebullioscopy measurements of the soluble part of the polymers were carried out in THF at 25&amp / #61616 / C. Scanning electron microscopy were used for morphology investigations of the polymers. Four probe conductivity measurements showed that electrical conductivity of the polymers increased according to the metallic conductivity of the metal at the center of the phthalocyanine units. When doped with iodine, the polymer samples showed 104 fold increase in their conductivities. Current-Voltage (I-V) measurements showed that the polymers were optically sensitive and semiconductors. Electrochemical analysis of the soluble part of the polymers were determined in tributylamine perchlorite+dichloromethane mixture utilizing cyclic voltammetry (CV).

Les semi-conducteurs moléculaires ont permis la réalisation de dispositifs électroniques, tels que transistors à effet de champ, diodes et autres hétérojonctions. Les matériaux ambipolaires, capables de transporter tant les charges positives que négatives, conduisent à des dispositifs aux propriétés particulières. L’objet de cette thèse est de synthétiser de nouveaux matériaux moléculaires ambipolaires et de développer des dispositifs électroniques originaux, en particulier pour des applications dans le domaine des capteurs de gaz. Nous nous intéressons aux molécules compatibles avec des mises en forme par des techniques dites de solution processing, en particulier des métallo-phtalocyanines. / The molecular semiconductors have enabled the production of electronic devices such as field effect transistors, diodes and other heterojunctions. The ambipolar materials, capable of carrying both positive charges and negative, result in devices with special properties. The purpose of this thesis is to synthesize new ambipolar materials develop original electronic devices, especially for applications in the field of gas sensors. We are interested in molecules capable to lead to thin films with low temperature techniques known as solution processing, particularly metallo-phthalocyanines.

abstract: The absorption spectra of metal-centered phthalocyanines (MPc's) have been investigated since the early 1960's. With improved experimental techniques to characterize this class of molecules the band assignments have advanced. The characterization remains difficult with historic disagreements. A new push for characterization came with a wave of interest in using these molecules for absorption/donor molecules in organic photovoltaics. The use of zinc phthalocyanine (ZnPc) became of particular interest, in addition to novel research being done for azaporphyrin analogs of ZnPc. A theoretical approach is taken to research the excited states of these molecules using time-dependent density functional theory (TDDFT). Most theoretical results for the first excited state in ZnPc are in only limited agreement with experiment (errors near 0.1 eV or higher). This research investigates ZnPc and 10 additional porphyrin analogs. Excited-state properties are predicted for 8 of these molecules using ab initio computational methods and symmetry breaking for accurate time- dependent self-consistent optimization. Franck-Condon analysis is used to predict the Q-band absorption spectra for all 8 of these molecules. This is the first time that Franck-Condon analysis has been reported in absolute units for any of these molecules. The first excited-state energy for ZnPc is found to be the closest to experiment thus far using a range-separated meta-GGA hybrid functional. The theoretical results are used to find a trend in the novel design of new porphyrin analog molecules. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2014

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Agradecemos a compreensão. on 2016-06-29T14:40:22Z (GMT) / Submitted by CRISTIANE BECK null (cristiane.beck@unijui.edu.br) on 2016-06-30T16:18:06Z No. of bitstreams: 1 Tese completa biblioteca.pdf: 1543432 bytes, checksum: 57e5b0af047f27b0a54c7540e57780b4 (MD5) / Approved for entry into archive by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br) on 2016-06-30T19:32:07Z (GMT) No. of bitstreams: 1 beck_c_dr_bot.pdf: 1543432 bytes, checksum: 57e5b0af047f27b0a54c7540e57780b4 (MD5) / Made available in DSpace on 2016-06-30T19:32:07Z (GMT). No. of bitstreams: 1 beck_c_dr_bot.pdf: 1543432 bytes, checksum: 57e5b0af047f27b0a54c7540e57780b4 (MD5) Previous issue date: 2016-06-03 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / A Leishmaniose Visceral é uma doença infecciosa, de caráter zoonótico, emergente e de notificação obrigatória. No Brasil tem como agente o protozoário Leishmania infantum chagasi, e o principal reservatório é o cão (Canis familiaris). A transfusão sanguínea é muito utilizada na rotina da clínica, entretanto está associada a transmissão de doenças infecciosas. O objetivo deste estudo foi avaliar os efeitos do tratamento com a luz visível associada a ftalocianina de cloro-alumínio na inativação da Leishmania infantum chagasi em sangue canino, quando inoculados em hamsters (Mesocricetus auratus). Foram preparados 3 grupos experimentais compostos por 6 hamsters cada. O grupo controle recebeu sangue negativo para Leishmania, o grupo doença foi inoculado com sangue parasitado com Leishmania infantum chagasi e o grupo tratamento recebeu sangue parasitado tratado com luz visível associada a ftalocianina de cloro-alumínio. Os animais foram monitorados por 180 dias e então submetidos a avaliação clínica. Em seguida os animais foram anestesiados para a coleta de sangue por meio de punção intracardíaca e procedendo-se assim a eutanásia. O sangue foi colocado em microtubos e o soro separado por centrifugação e acondicionado a -30ºC, até a realização do teste de aglutinação direta. Após procedeu-se a coleta do fígado e baço para a realização da histopatologia. Outra parte destes órgãos e a medula óssea foram acondicionados em tubos livres de DNAse e RNAse, congelados a -30ºC até a realização da PCR e qPCR. Impressões do fígado e baço foram feitas em lâminas para a microscopia para verificar a presença das formas amastigotas do parasita. Após 180 dias os animais não apresentaram sinais clínicos e os exames sorológicos e parasitológicos foram negativos. Quanto ao exame macroscópico, alguns animais apresentaram hepato e esplenomegalia, já na análise histopatológica nenhum tecido analisado demonstrou formas amastigotas do parasita. Na avaliação da PCR o baço e a medula óssea de todos os hamsters, dos grupos doença e tratado, apresentaram amplificação da Leishmania infantum chagasi. Na qPCR ocorreu uma significativa diminuição (P<0,01) na parasitemia quando comparado ao grupo tratado com a luz visível associada a ftalocianina de cloro-alumínio, com o grupo que recebeu sangue parasitado sem tratamento. Com esses resultados é possível concluir que a luz visível associada a ftalocianina de cloro-alumínio reduz a parasitemia da Leishmania infantum chagasi em sangue canino. / Visceral Leishmaniasis is an emerging zoonotic infectious disease that requires mandatory reporting. In Brazil, it is caused by the protozoan Leishmania infantum chagasi, with dogs as main reservoir (Canis familiaris). Blood transfusion is frequently used in clinical routine, however it is associated with the transmission of infectious diseases. The aim of this study was to evaluate the effects of treatment with visible light associated with chloro-aluminium phthalocyanine on the inactivation of Leishmania infantum chagasi in canine blood, when inoculated in hamsters (Mesocricetus auratus). Three experimental groups consisted of six hamsters each. The control group received blood negative for L. infantum chagasi, the diseased group was inoculated with blood infected with L. infantum chagasi, and the treatment group received infected blood previously subjected to therapy with visible light associated with chloroaluminium phthalocyanine. The animals were observed for 180 days and then subjected to clinical evaluation. Then the animals were anesthetized for blood collection through intracardiac puncture and were euthanized. The blood was placed into microtubes and the serum was separated by centrifugation and stored at -30 ° C until the direct agglutination test was performed. After, liver and spleen collection was performed to histopathological examination. Another part of these organs and bone marrow were placed in tubes DNase and RNase free, and frozen at -30°C until the PCR and qPCR were performed. Imprints of liver and spleen were performed on slides for microscopy to verify the presence of amastigotes of the parasites. After 180 days the animals showed no clinical signs and serologic and parasitological tests were negative. During pathological examination, some animals showed hepatomegaly and splenomegaly; under microscopic analysis, any tissue showed amastigote forms of the parasite. In the PCR evaluation of spleen and bone marrow, all hamsters from diseased and treated groups showed amplification of Leishmania infantum chagasi. Results from q-PCR revealed a significant decrease (P <0.01) in the number of parasites in the group inoculated with blood subjected to chloro-aluminium photodynamic therapy, compared to the group inoculated with parasitized blood that had not been subjected to photodynamic therapy. With these results it is possible to conclude that visible light associated with chlorine-aluminum phthalocyanine reduces parasitaemia of Leishmania infantum chagasi in canine blood. / FAPESP: 2014/03353-4

abstract: Natural photosynthesis dedicates specific proteins to achieve the modular division of the essential roles of solar energy harvesting, charge separation and carrier transport within natural photosynthesis. The modern understanding of the fundamental photochemistry by which natural photosynthesis operates is well advanced and solution state mimics of the key photochemical processes have been reported previously. All of the early events in natural photosynthesis responsible for the conversion of solar energy to electric potential energy occur within proteins and phospholipid membranes that act as scaffolds for arranging the active chromophores. Accordingly, for creating artificial photovoltaic (PV) systems, scaffolds are required to imbue structure to the systems. An approach to incorporating modular design into solid-state organic mimics of the natural system is presented together with how conductive scaffolds can be utilized in organic PV systems. To support the chromophore arrays present within this design and to extract separated charges from within the structure, linear pyrazine-containing molecular ribbons were chosen as candidates for forming conductive linear scaffolds that could be functionalized orthogonally to the linear axis. A series of donor-wire-acceptor (D-W-A) compounds employing porphyrins as the donors and a C60 fullerene adduct as the acceptors have been synthesized for studying the ability of the pyrazine-containing hetero-aromatic wires to mediate photoinduced electron transfer between the porphyrin donor and fullerene acceptor. Appropriate substitutions were made and the necessary model compounds useful for dissecting the complex photochemistry that the series is expected to display were also synthesized. A dye was synthesized using a pyrazine-containing heteroaromatic spacer that features two porphyrin chromophores. The dye dramatically outperforms the control dye featuring the same porphyrin and a simple benzoic acid linker. A novel, highly soluble 6+kDa extended phthalocyanine was also synthesized and exhibits absorption out to 900nm. The extensive functionalization of the extended phthalocyanine core with dodecyl groups enabled purification and characterization of an otherwise insoluble entity. Finally, in the interest of incorporating modular design into plastic solar cells, a series of porphyrin-containing monomers have been synthesized that are intended to form dyadic and triadic molecular-heterojunction polymers with dedicated hole and electron transport pathways during electrochemical polymerization. / Dissertation/Thesis / Ph.D. Chemistry 2013