Over the last few decades, bulk-heterojunction organic photovoltaic devices comprising an intimately mixed donor-acceptor blend have gained serious attention due to their potential for being cheap, light weight, flexible and environmentally friendly. In this thesis, APFO-3/PCBM bulk-heterojunction based organic photovoltaic devices with an inverted layer sequence were investigated systematically. Doctor blade coating is a technique that is roll-to-roll compatible and cost efficient and has been used to fabricate the solar cells. Initial studies focused on optimization of the electrodes. A thin film of the conductive polymer PEDOT:PSS was chosen to be the transparent anode. Different PEDOT:PSS films with respect to the film thickness and deposition temperature were characterized in terms of conductivity and transmission. Decent conductance and transmittance were obtained in the films deposited with wet film thickness setting of 35 μm, The cathode was fabricated from a metal bilayer comprising Al and Ti with an area about 1 cm2, and the best-working cathodes contained a 70 nm thick Al layer covered by a thin Ti layer of about 10 -15 nm. Optimized coating temperature and wet film thickness settings for the active layer and PEDOT:PSS layer were experimentally determined. The highest efficiency of the APFO-3/PCBM based inverted solar cells fabricated by doctor blading was 0.69%, which exceeded the efficiency of spin-coated inverted cells. A higher efficiency (0.8 %) was achieved by adding a small amount of high molecular weight polystyrene to the active layer. Morphological changes after adding of the polystyrene were observed by optical microscopy and AFM. A coating temperature dependent phase separation of the APFO-3/PCBM/polystyrene blend was found.

This project is an extension of a pre-existing simulation program (‘Simulation_2dioden’). This simulation program was first developed in Konarka Technologies. The main purpose of the project ‘Simulation_2dioden’ is to calibrate the values of different parameters like, Shunt resistance, Series resistance, Ideality factor, Diode current, epsilon, tau, contact probability, AbsCT, intensity, etc; This is one of the curve fitting procedure’s. This calibration is done by using different equations. Diode equation is one of the main equation’s used in calculating different currents and voltages, from the values generated by diode equation all the other parameters are calculated. The reason for designing this simulation_2dioden is to calculate the values of different parameters of a device and the researcher would know which parameter effects more in the device efficiency, accordingly they change the composition of the materials used in the device to acquire a better efficiency. The platform used to design this project is ‘Microsoft Excel’, and the tool used to design the program is ‘Visual basics’. The program could be otherwise called as a ‘Virtual Solar cell’. The whole Virtual Solar cell is programmed in a single excel sheet. An Automated working solution is suggested which could save a lot of time for the researchers, which is the main aim of this project. To calibrate the parameter values, one has to load the J-V characteristics and simulate the program by just clicking one button. And the parameters extracted by using this automated simulation are Parallel resistance, Series resistance, Diode ideality, Saturation current, Contact properties, and Charge carrier mobility. Finally, a basic working solution has been initiated by automating the simulation program for calibrating the parameter values.

We proposed a flexible electronics with functional poly (arylene ether)s and discotic liquid crystal. Firstly, we provided a series of the PAE polymer with remarkable thermal stability and high optical transmittance. The PAEs were synthesized via nucleophilic displacement as polymerization on a 2-trifluoromethyl-activated bisfluoro monomer, which reacted with bisphenols. Thermal analysis indicated the PAEs possessed a high glass transition point of ~300¢J and the decomposition temperature Td=500¢J at a weight loss of 5%. Additionally, high transmittance of 85%, low dielectric constant of ~2.0, and well mechanical property of the PAE films were experimentally verified, as a high potential substrate for flexible electronics. Two kind of device structure has been prepared, were organic thin film solar cell and Dye sensitized solar cell. Furthermore, we provided the self-assembled triphenylene-based liquid crystal and its polymer derivative to apply for photovoltics. The 2, 3, 6, 7-tetra-6-octyloxydibenzo[a,c]phenazine-11-carboxylic group and the polymer of merging with disc-unit and polyacrylamide. Both show a highly isotropic phase transition point of ~270¢J and the decomposition temperature Td~450¢J at a weight loss of 5%. The specific absorption in visible light region was at 200 - 450 nm. A distinct self-arrangement of columnar array was investigated by optical textures. The self-arranged pathway enhanced carrier mobility due to £k-£k conjugation in hexagonal column stacking. Finally, the PAEs and DLC materials applied to thin film solar cell (ITO/PEDOT:PSS/DLC-PAM/P3HT:PCBM/Al) as hole transporting layer. The photo-conversion efficiency was strong depending on organic compounds, such as molecular structure, photo-physic and chemical properties. On the basis of integrated characteristics, it suggested a high potential as flexible electronics for photovoltics.

This thesis studied on the research of how conducting polymer polyaniline can be used in the buffer layer of organic solar cell. There are two methods used.¡]1¡^Using spin-coating to make film of polyaniline solution.¡]2¡^Polymerizing aniline on the substrate directly by electrochemical polymerization. The electrochemical method is separated into cyclic voltammetry and potentiostatic method respectively. The latter method which improved the disadvantage of infractable thick film and low electric conductivity of polyaniline for spin-coating is chosen as the preparation method for polyaniline films. We discuss of the photoelectric characteristics and surface morphologies of polyaniline film and to make a solar cell base on Poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester measured with AM 1.5G 100 mW/cm2 solar light simulation. This research combine above-mentioned results to use potentiostatic method to polymerize polyaniline on the PEDOT¡GPSS into a compound electrode and to replace currently popular ITO positive pole in a organic solar component. The structure is PEDOT¡GPSS/PANI/P3HT¡GPCBM/Al. By electroplating polyaniline, it can enhance the electric conductivity of the film of PEDOT¡GPSS from 1 S/cm to 154 S/cm, furthermore, to reach 1.06% of photoelectric conversion efficiency and creates a new possibility of preparing a flexible organic solar cell.

Three new azobenzene containing conjugated monomers were designed and synthesized. Resulting monomers were characterized by means of 1H NMR and 13C NMR techniques. Monomers (E)-1,2-bis(4-(thiophen-2-yl)phenyl)diazene (M1), (E)-1,2-bis(4-(4-hexylthiophen-2-yl) phenyl) diazene (M2) and (E)-1,2-bis(2-fluoro-4-(4-hexylthiophen-2-yl)phenyl) diazene (M3) were electrochemically polymerized using cyclic voltammetry to give polymers P1, P2 and P3. The polymers were subjected to spectroelectrochemical and kinetic studies in order to obtain information about their elecrochromic characteristics. P1 and P2 were pale-yellow in their neutral states and blue in oxidized states while P3 showed multichromic property due to having polaron bands in visible region of the spectrum. Addition of fluorine atoms to the backbone of P3, lowered the LUMO level of P3 thus gained the polymer n-doping property. In the second part of this thesis poly((9,9-dioctylfluorene)-2,7-diyl-(4,7-bis(thien-2-yl) 2-dodecyl-benzo[1,2,3]triazole)) (PFTBT) polymer was mixed with common electron acceptor Phenyl-C61-butyric acid methyl ester (PCBM) and used in organic solar cell applications. Active layers containing PFTBT and PCBM were spin casted on ITO coated substrates at varying rotational speeds to obtain active layer thicknesses having different values. Thickness of the active layer was optimized so was the efficiency of organic solar cells. As a result of this optimization study, efficiency of PFTBT containing organic solar cells were increased to 1.06% which is a higher value than previosly reported literature results.

Organic solar cells promise electricity generation at very low cost, and higher installation flexibility as compared to inorganic solar cells. The lower cost is achieved by cheaper semiconductors and easier manufacturing processes. The flexibility is naturally given by these ultra-thin, amorphous layers. Also the power conversion efficiency can be high enough for many applications. The organic molecules have to withstand the constant excitation by photons, transport of energy in form of excitons and charge. A small but significant amount of these photons has energy over the absorption gap, the excess of energy must be released without breaking the molecular bonds. In consequence, the solar cells can also heat up to temperatures at above 80°C. The objective of this work is to answer the question if the small molecules organic solar cells can be stable enough to operate under a very long time. The stability of organic doped layers in an organic solar cell is also addressed. This work starts with a general introduction followed by the description of the experimental procedures. The aging experiments of the solar cell were done with a self developed equipment. The fabrication of this equipment (a set of measurement boxes) was necessary to maintain the conditions, under which a solar cell can be aged, as constant as possible. The measurement boxes were used to control the electrical load of the cell, its temperature, the illumination intensity, and its electric connection to the IxV measurement equipment. A software package was also developed to control the equipment and to facilitate the work and visualization of the high volume of collected data. The model solar cells chosen for the aging experiments were donor-acceptor heterojunctions devices formed with the well-known materials C60 and ZnPc. Two basic different structures were analyzed, because they offered reasonable performance and potentially long lifetime: the flat heterojunction (FHJ) and the mixed heterojunction in a Metal-Insulator-p-Semiconductor (m-i-p) configuration. Variations of the FHJ and of the m-i-p structures are also used to verify the limits of the stability of electrically p- and n- doped organic semiconducting layers. The least stable solar cells are the FHJ devices. These devices show a fast initial decrease of all their characteristic conversion parameters but the Voc. After a few hundred hours, the saturation current (current under a reverse bias of 1 V) was almost stable. The saturation current is related to the number of absorbing centers, the decrease indicates that the degradation of the absorbing centers has stopped. With wavelength resolved external quantum efficiency measurements and chemical analysis, it was found that the degradation is related to the oxidation of C60. It was also shown that the use of organic dopants do not significantly affect the lifetime. The results show that the m-i-p solar cells are more stable than the FHJ devices. They are also stable under high temperatures up to 105°C. Outdoor testing also showed that the solar cells remained chemically, electrically and mechanically stable during a 900 h test.

<p>This project is an extension of a pre-existing simulation program (‘Simulation_2dioden’). This simulation program was first developed in Konarka Technologies. The main purpose of the project ‘Simulation_2dioden’ is to calibrate the values of different parameters like, Shunt resistance, Series resistance, Ideality factor, Diode current, epsilon, tau, contact probability, AbsCT, intensity, etc; This is one of the curve fitting procedure’s. This calibration is done by using different equations. Diode equation is one of the main equation’s used in calculating different currents and voltages, from the values generated by diode equation all the other parameters are calculated.</p><p>The reason for designing this simulation_2dioden is to calculate the values of different parameters of a device and the researcher would know which parameter effects more in the device efficiency, accordingly they change the composition of the materials used in the device to acquire a better efficiency. The platform used to design this project is ‘Microsoft Excel’, and the tool used to design the program is ‘Visual basics’. The program could be otherwise called as a ‘Virtual Solar cell’. The whole Virtual Solar cell is programmed in a single excel sheet.</p><p>An Automated working solution is suggested which could save a lot of time for the researchers, which is the main aim of this project. To calibrate the parameter values, one has to load the J-V characteristics and simulate the program by just clicking one button. And the parameters extracted by using this automated simulation are Parallel resistance, Series resistance, Diode ideality, Saturation current, Contact properties, and Charge carrier mobility.</p><p>Finally, a basic working solution has been initiated by automating the simulation program for calibrating the parameter values.</p>

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第19007号 / 工博第4049号 / 新制||工||1623 / 31958 / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 伊藤 紳三郎, 教授 赤木 和夫, 教授 辻井 敬亘 / 学位規則第4条第1項該当

A hole-collecting interlayer layer for organic solar cells, NiO, processed by atomic layer deposition (ALD) was studied. ALD-NiO film offered a novel alternative to efficient hole-collecting interlayers in conventional single-junction organic solar cells. Next, surface modifications with aliphatic amine group containing polymers for use as electron-collecting interlayers were studied. Physisorption of the polymers was found to lead to large reduction of the work function of conducting materials. This approach provides an efficient way to provide air-stable low-work function electrodes for organic solar cells. Highly efficient inverted organic solar cells were demonstrated by using the polymer surface modified electrodes. Lastly, charge recombination layers of the inverted tandem organic solar cells were studied. Efficient charge recombination layers were realized by using the ALD and the polymer surface modification. The charge recombination layer processed by ALD provided enhanced electrical and barrier properties. Furthermore, the polymer surface modification on the charge recombination layers showed large work function contrast, leading to improved inverted tandem organic solar cells. The inverted tandem organic solar cells with the new charge recombination layer showed fill factor over 70% and power conversion efficiency over 8%.

abstract: Thin films have been widely used in various applications. This research focuses on the characterization of novel thin films in the integrated circuits and photovoltaic techniques. The ion implanted layer in silicon can be treated as ion implanted thin film, which plays an essential role in the integrated circuits fabrication. Novel rapid annealing methods, i.e. microwave annealing and laser annealing, are conducted to activate ion dopants and repair the damages, and then are compared with the conventional rapid thermal annealing (RTA). In terms of As+ and P+ implanted Si, the electrical and structural characterization confirms that the microwave and laser annealing can achieve more efficient dopant activation and recrystallization than conventional RTA. The efficient dopant activation in microwave annealing is attributed to ion hopping under microwave field, while the liquid phase growth in laser annealing provides its efficient dopant activation. The characterization of dopants diffusion shows no visible diffusion after microwave annealing, some extent of end range of diffusion after RTA, and significant dopant diffusion after laser annealing. For photovoltaic applications, an indium-free novel three-layer thin-film structure (transparent composited electrode (TCE)) is demonstrated as a promising transparent conductive electrode for solar cells. The characterization of TCE mainly focuses on its optical and electrical properties. Transfer matrix method for optical transmittance calculation is validated and proved to be a desirable method for predicting transmittance of TCE containing continuous metal layer, and can estimate the trend of transmittance as the layer thickness changes. TiO2/Ag/TiO2 (TAgT) electrode for organic solar cells (OSCs) is then designed using numerical simulation and shows much higher Haacke figure of merit than indium tin oxide (ITO). In addition, TAgT based OSC shows better performance than ITO based OSC when compatible hole transfer layer is employed. The electrical and structural characterization of hole transfer layers (HTLs) in OSCs reveals MoO3 is the compatible HTL for TAgT anode. In the end, the reactive ink printed Ag film for solar cell contact application is studied by characterizing its electromigration lifetime. A percolative model is proposed and validated for predicting the resistivity and lifetime of printed Ag thin films containing porous structure. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2017