The present work addresses issues related to the derivation of reduced models of atomistic systems, their statistical calibration, and their relation to atomistic models of materials. The reduced model, known in the chemical physics community as a coarse-grained model, is calibrated within a Bayesian framework. Particular attention is given to developing likelihood functions, assigning priors on coarse-grained model parameters, and using data from molecular dynamics representations of atomistic systems to calibrate coarse-grained models such that certain physically relevant atomistic observables are accurately reproduced. The developed Bayesian framework is then applied in three case studies of increasing complexity and practical application. A freely jointed chain model is considered first for illustrative purposes. The next example entails the construction of a coarse-grained model for a liquid heptane system, with the explicit design goal of accurately predicting a vapor-liquid transfer free energy. Finally, a coarse-grained model is developed for an alkylthiophene polymer that has been shown to have practical use in certain types of photovoltaic cells. The development therein employs Bayesian decision theory to select an optimal CG potential energy function. Subsequently, this model is subjected to validation tests in a prediction scenario that is relevant to the performance of a polyalkylthiophene-based solar cell. / text

In the recent years area organic photovoltaics is generating a lot of interests because whole process of synthesis and fabrication is less energy intensive process as well as it is cost effective compared to conventional inorganic Si based photovoltaic technology. This work mainly deals with the fabrication and optimization of device fabrication conditions for organic photovoltaic materials. In first part of the work, the solar cell fabrication conditions were optimized for the commonly used system P3HT – PCBM. The fabricated device was optimized for the solvents used for the active material, concentration of the active material solution, donor- acceptor ratio of the active material, annealing conditions of the active layer and the metal evaporation conditions for the cathode. All the optimization procedures were carried out in controlled atmosphere to minimize the environmental effect inference during fabrication of the solar cell devices. All the characterization was carried out at ambient conditions. The efficiency of the solar cell was improved from 0.009% to 6.2%. the environmental stability of the fabricated devices were carried out after encapsulating it with epoxy based resin in both ambient conditions as well as extreme conditions like 85% RH at 25°C inside the humidity chamber. It was observed that both the data matches well with each other indicating proper encapsulation required to safe guard the device for the better performance over the period of time. Second part of this work mainly deals with understanding the structure property relationship of thiophene based donor- acceptor- donor molecule 2,5-dithienyl-3,4-(1,8-naphthylene) cyclopentadienone (DTCPA), which is highly crystalline, low band gap organic molecule which absorbs over entire visible region of the solar spectra. DTCPA crystals of various morphologies were prepared by various recrystallization routes. It was observed that macro scale morphology of these crystals differs from each other. Also depending on the method of recrystallization sizes of the crystals also varies. All the recrystallized DTCPA shows strong orientation toward (001) direction. However, it was observed that lattice parameters of these crystals slightly differ from each other owing to the recrystallization methodology. These variations in crystal parameters are more than 0.02 which is significant. It was also observed that the crystallite sizes depend on the recrystallization routes. Slow evaporation of concentrated solution (SEC) grown crystals has the larger crystallite size of 170nm. It was observed that absorption range of these crystals slightly differ from each other owing to the change in the crystallite sizes and crystal parameters. Third part of this work deals with the fabrication and optimization of thermal evaporation process of DTCPA for photovoltaic applications. DTCPA is stable at higher temperatures as well as has sharp melting point which make it ideal candidate for thermal evaporation. In this work films of DTCPA were fabricated for various evaporation rates by thermal evaporation technique. Chemical integrity of the molecules upon evaporation is found to be intact as observed from FTIR spectroscopy. XRD shows that at lower (25 W/m2) as well as higher (40 W/m2) films are oriented to (001), (400) as well as (311) directions, at 30 W/m2 and 35 W/m2 there is a strong orientation towards (311) and (001) directions respectively. Photo luminescence studies indicate that there is strong 410 nm emission for films deposited at the power of 25 W/m2 and 40 W/m2. Microscopic studies confirm that morphology is dependent on the deposition rates as it changes with the change in deposition rate. This in turn reflects in the device characteristics of these films. It was observed that films deposited at high deposition rates show better device characteristics with high VOC and current density values. All these device fabrication and characterizations were carried out in ambient conditions. Fourth part of this work deals with P3HT - DTCPA composites which exhibit wide range of light absorption. It was observed that DTCPA act as nucleating centers for the P3HT molecules and increases crystallinity in the composite. Furthermore, DTCPA helps in exciton separation because of donor and acceptor moieties present in the molecule. It also helps in charge transportation because of its crystalline nature and further it induces molecular ordering in the P3HT matrix. The band diagram of P3HT- DTCPA suggests that the band edges of both materials are ideal for charge separation. In addition, crystalline nature of the DTCPA molecule helps in effective charge transportation. J-V characteristics shows that there is large built in potential in the devices from these blends leading to large Voc. Composites with lower DTCPA loadings show higher efficiency than with higher loadings. These devices were prepared in ambient conditions and needs to be optimized for obtaining better device properties. In the fifth part of the work two types of system were studied to understand the band edge matching on the photovoltaic properties, carbazole based copolymers and DTCPA based copolymers. In the case of carbazole based copolymers it was observed that by copolymerizing carbazole with thiophene based derivatives lowers the band gap and modifies the HOMO and LUMO levels for better suit for the photovoltaic device fabrication. It was observed that that is two orders of improvements in the efficiency by co polymerizing carbazole with benzothiodizole as improves the JSC and VOC. Also the copolymerization of carbazole with both benzothiodiazole and bithiophene results in better light harvesting as the optical band gap was lowered. In the case of DTCPA copolymers with DTBT and DHTBT as both are random copolymers the solubility was low as well as their HOMO band edge was mismatched with the PEDOT: PSS which is a hole transport layer. However, the alternate polymerization of DTCPA with DTBT improved the band edge matching and also the solubility. As a result there was tenfold improvement in the charge collection and hence the efficiency was improved from 0.02% to 2.4%. Many of the conducting polymers have good material property but poor filmability. In the sixth part of this work deals with fabrication of device quality films by alternate deposition technique like pulsed laser deposition. Two types of system were studied in this work (i) polypyrrole- MWCNT nanocomposites and (ii) Poly DTCPA polymer. In both the cases it was observed that chemical integrity of the polymer retained during ablation. PolyDTCPA films were fabricated by pulsed laser deposition by both IR (Nd-YAG) and UV (KrF) laser source. Morphological studies indicate that IR laser ablated films were particulate in nature whereas UV laser ablated films were grown as continuous layers as polyDTCPA absorbs better in UV region. As a result the IV characteristics indicate that IR laser ablated films are resistive in nature and UV laser ablated films are good rectifiers indicating the suitability of the process for fabrication of device quality films.

In recent years, organic photovoltaics (OPVs) have attracted considerable attention as a potential source of renewable energy over traditional materials due to their light weight, low production cost, mechanically stability and compatibility with flexible substrates in roll to roll processing for high volume production. In the OPVs interface plays an important role in determining the performance of the device. Interface signifies formation of efficient contact with electrode, film, and transport of free charge carrier, which results in better performance in the device. Interface engineering also helps in improving mechanical robustness of the device. Hence, understanding of interface, modification and its evaluation is important in fabrication of efficient device. In this thesis interface is modified such that the performance of the device can be improved (chapter 3 and chapter 4). In Chapter 5 and chapter 6 interface is modified such that device can be fabricated on uncommon substrate. Fabrication of device on uncommon substrates (fiber reinforced plastic and flexible glass substrate), has unique challenges. In chapter 5 and chapter 6, we look at how interface is modified to overcome the challenges associated and also understand the role of interface in improving the performance of device on such substrates is discussed. In Chapter 1 we discuss about working of organic solar cells and the challenges associated in device fabrication. Understanding of interface to overcome challenges associated is explained. It also covers brief introduction to the succeeding chapters discussed in the thesis and its recent developments. To understand the properties of interface and to analyze device performance various characterization techniques have been used are discussed in chapter 2. This chapter also covers the materials and general device fabrication techniques used in this thesis. In chapter 3, a narrow bandgap (NBG) polymer used as a near IR sensitizer in P3HT: PCBM blend. Since, P3HT with a band gap of ~1.9 eV, the commonly used p-type material absorbs approximately ~25 % of incident light. Hence, MP2 (NBG polymer) is used along with P3HT: PCBM in active layer to form a ternary blend, which helps in increased absorption. Basic properties of MP2 are evaluated using UV-visible spectroscopy, differential scanning calaorimetry(DSC), thermogravimetric analyser (TGA), gel permeation chromatography (GPC) and photoluminescence (PL) techniques. To evaluate enhanced absorption of ternary UV-visible spectroscopy is carried out. Charge transfer from one moiety to other in ternary blend is evaluated using PL and Ttime resolved microwave conductivity (TRMC). Morphology of the ternary is assessed using atomic force microscope (AFM) and structural characterization is carried out by X-ray diffraction (XRD). Performance of the device is evaluated by current-voltage (J-V) characterizations. Further improved performance is supported by external quantum efficiency (EQE). Charge extraction with linear increasing voltage (CELIV) of the device is done to evaluate the recombination mechanism in the device and to assess the performance of the device. One-dimensional (1D) ZnO nanostructures provide direct paths for charge transport, and also offer large interfacial area to make them an ideal electron transport layer. In chapter 4 highly aligned ZnO nanorods is used as electron transport layer in OPV. Growth of ZnO nanorods is two-step processes, growing seed layer and growing ZnO nanorods from hydrothermal process using an appropriate seed layer. Two different soft-chemical solution- growth methods (upward and downward) are developed to fabricate self-assembled, oriented ZnO nanorods. Substrate mounting, surface properties and optical transmittance are optimized by varying the nanorods growth conditions. Further the ZnO nanorods are UV ozone treated and its effect on performance of nanostructured buffer layer based device is evaluated. In Chapter 5 OPV is fabricated on an opaque FRP substrate. Fabrication of OPV device on opaque substrate plastic is unique and hence understanding various properties is vital. Such devices fabrication require bottom up approach, with transparent electrode as the top electrode and metal electrode on the surface of FRP. FRP has inherent rough surface of about few microns RMS roughness. In order to reduce the roughness of the substrate FRP was planarized. The planarized layer is chosen, such that it chemically binds with the substrate. The chemical interaction between substrate and planarizing coating is evaluated by FTIR and Raman spectroscopy. The binding of planarized layer and FRP is evaluated using nanoscratch technique and surface energies are studied using contact angle measurements. In addition, adhesion properties of the metal electrodes, which are deposited on planarized FRP are evaluated using nanoscratch technique. Fabrication of OPV requires a top transparent electrode. Simple spin coating technique is used to optimize the top electrode. The property of top electrode is evaluated using UV-visible spectroscopy for transmittance, and sheet resistance of the electrode is characterized. OPV device is fabricated on planarized FRP substrate using optimized top transparent electrode and its PV properties is evaluated. Performance of the device is evaluated for two different bottom electrodes and further performance of device is enhanced using buffer layers. Usually flexible OPVs are fabricated on plastic substrate such as PET, PEN. However they are not structurally stable at high temperatures and have high oxygen and moisture Permeability. In Chapter 6 Organic based photovoltaic devices were fabricated on flexible glass. Flexible glass has high strength and it is also known for low oxygen and moisture permeability. Fabrication of device on flexible glass has never been done before and hence, generation of data is necessary for commercialization of the technology. Device fabrication is optimized by using two different transparent conducting layers (ITO- sputter deposited, PEDOT: PSS-solution processed) and device performance was evaluated for both. Since the substrate is flexible in nature understanding the performance of the device during flexing is important. For this 2-parallel plate flexural apparatus is fabricated for in-situ measurements along with current voltage measurements. These devices are flexed cyclically and performance of device is evaluated. Therefore, work discussed in the thesis show by modifying the interface of the device, and understanding various interfaces of the device is crucial for improving the performance of the device. Also by engineering the interface, devices can be fabricated on various types of substrate.

L’exploitation des couches interfaciales à base de d’oxydes métalliques ouvre des perspectives nouvelles dans le domaine des cellules photovoltaïques organiques (PVOs).Cette thèse s’inscrit dans le développement, la caractérisation et l’analyse de couches interfaciales, à base d’oxyde de zinc (ZnO), déposées par pulvérisation cathodique, dans l’élaboration de dispositifs solaires compatibles avec des substrats flexibles et des procédés « roll-to-roll ». Après un état de l’art du domaine, une première étude sera consacrée à l'apport et à l’optimisation des dépôts par pulvérisation cathodique des films de ZnO sur des couches actives de P3HT:PCBM dans le cas de structures conventionnelles. Une seconde partie mettra en évidence l'importance des procédés de recuit des couches de ZnO déposées sur des substrats flexibles ou rigides à base d’ITO pour des structures inverses de cellules PVOs flexibles. Suite à ces études, l’élaboration de ces dispositifs sera testée et validée à partir de techniques inspirées de la lithographie douce. L’interfaçage des films de ZnO avec de nouveaux matériaux tel que le graphène sera également abordé dans ces recherches. / Exploring interfacial layers based on metal oxides opens new perspectives in the field of organic photovoltaic (OPV). This thesis takes place in development, characterization and analysis of Zinc Oxide (ZnO) based interfacial layers, deposited by sputtering in the preparation of solar cells devices compatible with flexible substrates and "roll-to-roll" process. After a state of art, the first study will focus on contribution and optimization of ZnO films sputtered on active layer (P3HT:PCBM) for conventional structures. A second study will highlight the importance of annealing processes of ZnO layers deposited on flexible and rigid substrates based on ITO for inverse flexible solar cells. Following these studies, the development of the devices will be tested and validated using printing techniques inspired from soft lithography. Finally, new materials as graphene will be interfaced with ZnO layers and discuss in this research.