Charge separation and recombination in novel polymeric absorber materials for organic solar cells : a photophysical study

In dieser Dissertation wird die Ladungsträgergeneration und -rekombination in neuen polymeren Absorbermaterialien für organische Solarzellen untersucht. Das Verständnis dieser Prozesse ist wesentlich für die Entwicklung neuer photoaktiver Materialsysteme, die hohe Effizienzen erzielen und organische Solarzellen konkurrenzfähig im Bereich der erneuerbaren Energien machen. Experimentell verwendet diese Arbeit hauptsächlich die Methode der transienten Absorptionsspektroskopie, die sich für die Untersuchung photophysikalischer Prozesse auf einer Zeitskala von 100 fs bis 1 ms als sehr leistungsfähig erweist. Des Weiteren wird eine soft-modeling Methode vorgestellt, die es ermöglicht, photophysikalische Prozesse aus einer gemessenen transienten Absorptions-Datenmatrix zu bestimmen, wenn wenig a priori Kenntnisse der Reaktionskinetiken vorhanden sind. Drei unterschiedliche Donor:Akzeptor-Systeme werden untersucht; jedes dieser Systeme stellt eine andere Herangehensweise zur Optimierung der Materialien dar in Bezug auf Lichtabsorption über einen breiten Wellenlängenbereich, effiziente Ladungstrennung und schnellen Ladungstransport. Zuerst wird ein Terpolymer untersucht, das aus unterschiedlichen Einheiten für die Lichtabsorption und den Ladungstransport besteht. Es wird gezeigt, dass es möglich ist, den Fluss angeregter Zustände vom Chromophor auf die Transporteinheit zu leiten. Im zweiten Teil wird der Einfluss von Kristallinität auf die freie Ladungsträgergeneration mit einer Folge von ternären Mischungen, die unterschiedliche Anteile an amorphem und semi-kristallinem Polymer enthalten, untersucht. Dabei zeigt es sich, dass mit steigendem amorphen Polymeranteil sowohl der Anteil der geminalen Ladungsträgerrekombination erhöht als auch die nicht-geminale Rekombination schneller ist. Schlussendlich wird ein System untersucht, in dem sowohl Donor als auch Akzeptor Polymere sind, was zu verbesserten Absorptionseigenschaften führt. Die Rekombination von Ladungstransferzuständen auf der unter 100 ps Zeitskala stellt hier den hauptsächliche Verlustkanal dar, da freie Ladungsträger nur an Grenzflächen erzeugt werden können, an denen Donor und Akzeptor face-to-face zueinander orientiert sind. Darüber hinaus wird festgestellt, dass weitere 40-50% der Ladungsträger durch die Rekombination von Grenzflächenzuständen verloren gehen, die aus mobilen Ladungsträgern geminal gebildet werden.

Charge generation and recombination in solid-state dye-sensitized solar cells

Diese Doktorarbeit befasst sich mit Ladungsgeneration und – rekombination in Feststoff-Farbstoffsolarzellen, die spiro-OMeTAD als Lochleiter verwenden. Die vorliegende Arbeit ist in drei Fallstudien unterteilt: i.) Kern-erweiterte Rylen-Farbstoffe, ii.) ein Perylenmonoimid-Farbstoff und iii.) Donor-π verbrückte (Cyclopentadithiophen)-Akzeptor-Farbstoffe. Trotz ihres hohen molaren Extinktionskoeffizienten und der hohen Absorbanz der sensibilisierten Filme, zeigen einige dieser Farbstoffmoleküle nur geringe photovoltaischen Effizienzen. Um den Ursprung des geringen Wirkungsgrades herauszufinden, wurde breitbandige, ultraschnelle transiente Absorptionsspektroskopie an Solarzellen durchgeführt.rnInsbesondere die Auswirkungen verschiedender Ankergruppen, Dipolmomente, Photolumineszenzlebenszeiten, Lithium-Kationensensitivität und Ladungsträgerdynamik, die alle einen großen Einfluss auf den Wirkungsgrad der Solarzelle besitzen, wurden untersucht. In der ersten Fallstudie zeigte ein kurzer Rylen-Farbstoff aufgrund deutlich verlängerter Lebenszeiten die beste Effizienz im Vergleich zu größeren Kern-erweiterten Rylen-Farbstoffen. Die Lebenszeit wurde weiter reduziert, wenn Maleinsäure als Ankergruppe unter einer Ringöffnungsreaktion an die mesoporöse Oberfläche des Metalloxid-Halbleiters adsorbierte. Dies konnte mit Hilfe von Berechnungen mittels der Dichtefunktionaltheorie (DFT, B3LYP) auf die Differenz des Dipolmoments zwischen Grundzustand und angeregtem Zustand zurückgeführt werden. Die Berechnungen bekräftigen die unvorteilhafte Injektion von Ladungen durch die Änderung der Richtung des Dipolmoments, wenn eine Ringöffnung der Anhydridgruppe stattfindet. In der zweiten Studie zeigte das Perylenmonoimid-Derivat ID889 einen Wirkungsgrad von 4.5% in Feststoff-Farbstoffsolarzellen, wobei ID889 sogar ohne Zuhilfenahme eines Additivs in der Lage ist langlebige Farbstoffkationen zu bilden. Die Verwendung von Lithium-Kationen stabilisiert jedoch sowohl den Prozess der Ladungsgeneration als auch den der Ladungsregeneration. Des Weiteren wurde in ID889-sensitivierten Bauteilen kein reduktives Löschen beobachtet. Dabei wurde die Dynamik der Exzitonen mittels einer soft-modelling Methode Kurvenanalyse aus den Daten der transienten Absorptionsspektroskopie gewonnen. Zuletzt wurden Strukturen mit Cyclopentadithiophen(CPDT)-Baustein untersucht, die eine typische D-π-A Molekülstruktur bilden. FPH224 und 233 zeigten dabei eine bessere Effizienz als FPH231 und 303 aufgrund einer großen Injektionseffizienz (IE) und längerer Lebenszeit der angeregten Zustände. Dies kann auf reduktives Löschen in FPH231 und 303 zurückgeführt werden, wohingegen FPH224 und 233 einen moderaten Zerfall des Spirokationensignals zeigten.

Integrated solar energy and absorption cooling model for HVAC (heating, ventilating, and air conditioning) applications in buildings

The demands in production and associate costs at power generation through non renewable resources are increasing at an alarming rate. Solar energy is one of the renewable resource that has the potential to minimize this increase. Utilization of solar energy have been concentrated mainly on heating application. The use of solar energy in cooling systems in building would benefit greatly achieving the goal of non-renewable energy minimization. The approaches of solar energy heating system research done by initiation such as University of Wisconsin at Madison and building heat flow model research conducted by Oklahoma State University can be used to develop and optimize solar cooling building system. The research uses two approaches to develop a Graphical User Interface (GUI) software for an integrated solar absorption cooling building model, which is capable of simulating and optimizing the absorption cooling system using solar energy as the main energy source to drive the cycle. The software was then put through a number of litmus test to verify its integrity. The litmus test was conducted on various building cooling system data sets of similar applications around the world. The output obtained from the software developed were identical with established experimental results from the data sets used. Software developed by other research are catered for advanced users. The software developed by this research is not only reliable in its code integrity but also through its integrated approach which is catered for new entry users. Hence, this dissertation aims to correctly model a complete building with the absorption cooling system in appropriate climate as a cost effective alternative to conventional vapor compression system.

Minimizing residential distribution system operating costs through intelligently scheduled plug-in hybrid electric vehicle charging

Rising fuel prices and environmental concerns are threatening the stability of current electrical grid systems. These factors are pushing the automobile industry towards more effcient, hybrid vehicles. Current trends show petroleum is being edged out in favor of electricity as the main vehicular motive force. The proposed methods create an optimized charging control schedule for all participating Plug-in Hybrid Electric Vehicles in a distribution grid. The optimization will minimize daily operating costs, reduce system losses, and improve power quality. This requires participation from Vehicle-to-Grid capable vehicles, load forecasting, and Locational Marginal Pricing market predictions. Vehicles equipped with bidirectional chargers further improve the optimization results by lowering peak demand and improving power quality.

Quantum dot / optical protein bio-nano hybrid system biosensing

The integration of novel nanomaterials with highly-functional biological molecules has advanced multiple fields including electronics, sensing, imaging, and energy harvesting. This work focuses on the creation of a new type of bio-nano hybrid substrate for military biosensing applications. Specifically it is shown that the nano-scale interactions of the optical protein bacteriorhodopsin and colloidal semiconductor quantum dots can be utilized as a generic sensing substrate. This work spans from the basic creation of the protein to its application in a novel biosensing system. The functionality of this sensor design originates from the unique interactions between the quantum dot and bacteriorhodopsin molecule when in nanoscale proximity. A direct energy transfer relationship has been established between coreshell quantum dots and the optical protein bacteriorhodopsin that substantially enhances the protein’s native photovoltaic capabilities. This energy transfer phenomena is largely distance dependent, in the sub-10nm realm, and is characterized experimentally at multiple separation distances. Experimental results on the energy transfer efficiency in this hybrid system correlate closely to theoretical predictions. Deposition of the hybrid system with nano-scale control has allowed for the utilization of this energy transfer phenomena as a modulation point for a functional biosensor prototype. This work reveals that quantum dots have the ability to activate the bacteriorhodopsin photocycle through both photonic and non-photonic energy transfer mechanisms. By altering the energy transferred to the bacteriorhodopsin molecule from the quantum dot, the electrical output of the protein can be modulated. A biosensing prototype was created in which the energy transfer relationship is altered upon target binding, demonstrating the applicability of a quantum dot/bacteriorhodopsin hybrid system for sensor applications. The electrical nature of this sensing substrate will allow for its efficient integration into a nanoelectronics array form, potentially leading to a small-low power sensing platform for remote toxin detection applications.

STUDY OF HYBRID ELECTRIC VEHICLE BATTERY MODELING AND CONTROL USING AUTONOMIE

This report presents the research results of battery modeling and control for hybrid electric vehicles (HEV). The simulation study is conducted using plug-and-play powertrain and vehicle development software, Autonomie. The base vehicle model used for testing the performance of battery model and battery control strategy is the Prius MY04, a power-split hybrid electric vehicle model in Autonomie. To evaluate the battery performance for HEV applications, the Prius MY04 model and its powertrain energy flow in various vehicle operating modes are analyzed. The power outputs of the major powertrain components under different driving cycles are discussed with a focus on battery performance. The simulation results show that the vehicle fuel economy calculated by the Autonomie Prius MY04 model does not match very well with the official data provided by the department of energy (DOE). It is also found that the original battery model does not consider the impact of environmental temperature on battery cell capacities. To improve battery model, this study includes battery current loss on coulomb coefficient and the impact of environmental temperature on battery cell capacity in the model. In addition, voltage losses on both double layer effect and diffusion effect are included in the new battery model. The simulation results with new battery model show the reduced fuel economy error to the DOE data comparing with the original Autonomie Prius MY04 model.

Predictive control of hybrid vehicle powertrain for intelligent energy management

This thesis studies the minimization of the fuel consumption for a Hybrid Electric Vehicle (HEV) using Model Predictive Control (MPC). The presented MPC – based controller calculates an optimal sequence of control inputs to a hybrid vehicle using the measured plant outputs, the current dynamic states, a system model, system constraints, and an optimization cost function. The MPC controller is developed using Matlab MPC control toolbox. To evaluate the performance of the presented controller, a power-split hybrid vehicle, 2004 Toyota Prius, is selected. The vehicle uses a planetary gear set to combine three power components, an engine, a motor, and a generator, and transfer energy from these components to the vehicle wheels. The planetary gear model is developed based on the Willis’s formula. The dynamic models of the engine, the motor, and the generator, are derived based on their dynamics at the planetary gear. The MPC controller for HEV energy management is validated in the MATLAB/Simulink environment. Both the step response performance (a 0 – 60 mph step input) and the driving cycle tracking performance are evaluated. Two standard driving cycles, Urban Dynamometer Driving Schedule (UDDS) and Highway Fuel Economy Driving Schedule (HWFET), are used in the evaluation tests. For the UDDS and HWFET driving cycles, the simulation results, the fuel consumption and the battery state of charge, using the MPC controller are compared with the simulation results using the original vehicle model in Autonomie. The MPC approach shows the feasibility to improve vehicle performance and minimize fuel consumption.

Preparation of highly-ordered TiO₂ nanotube arrays and their applications in Dye-sensitized solar cells

Titanium oxide is an important semiconductor, which is widely applied for solar cells. In this research, titanium oxide nanotube arrays were synthesized by anodization of Ti foil in the electrolyte composed of ethylene glycol containing 2 vol % H2O and 0.3 wt % NH4F. The voltages of 40V-50V were employed for the anodizing process. Pore diameters and lengths of the TiO2 nanotubes were evaluated by field emission scanning electron microscope (FESEM). The obtained highly-ordered titanium nanotube arrays were exploited to fabricate photoelectrode for the Dye-sensitized solar cells (DSSCS). The TiO2 nanotubes based DSSCS exhibited an excellent performance with a high short circuit current and open circuit voltage as well as a good power conversion efficiency. Those can be attributed to the high surface area and one dimensional structure of TiO2 nanotubes, which could hold a large amount of dyes to absorb light and help electron percolation process to hinder the recombination during the electrons diffusion in the electrolyte.

SYNTHESIS OF GRAPHENE AND ITS APPLICATIONS FOR DYE-SENSITIZED SOLAR CELLS

Graphene, which is a two-dimensional carbon material, exhibits unique properties that promise its potential applications in photovoltaic devices. Dye-sensitized solar cell (DSSC) is a representative of the third generation photovoltaic devices. Therefore, it is important to synthesize graphene with special structures, which possess excellent properties for dye-sensitized solar cells. This dissertation research was focused on (1) the effect of oxygen content on the structure of graphite oxide, (2) the stability of graphene oxide solution, (3) the application of graphene precipitate from graphene oxide solution as counter electrode for DSSCs, (4) the development of a novel synthesis method for the three-dimensional graphene with honeycomb-like structure, and (5) the exploration of honeycomb structured graphene (HSG) as counter electrodes for DSSCs. Graphite oxide is a crucial precursor to synthesize graphene sheets via chemical exfoliation method. The relationship between the oxygen content and the structures of graphite oxides was still not explored. In this research, the oxygen content of graphite oxide is tuned by changing the oxidation time and the effect of oxygen content on the structure of graphite oxide was evaluated. It has been found that the saturated ratio of oxygen to carbon is 0.47. The types of functional groups in graphite oxides, which are epoxy, hydroxyl, and carboxylgroups, are independent of oxygen content. However, the interplanar space and BET surface area of graphite oxide linearly increases with increasing O/C ratio. Graphene oxide (GO) can easily dissolve in water to form a stable homogeneous solution, which can be used to fabricate graphene films and graphene based composites. This work is the first research to evaluate the stability of graphene oxide solution. It has been found that the introduction of strong electrolytes (HCl, LiOH, LiCl) into GO solution can cause GO precipitation. This indicates that the electrostatic repulsion plays a critical role in stabilizing aqueous GO solution. Furthermore, the HCl-induced GO precipitation is a feasible approach to deposit GO sheets on a substrate as a Pt-free counter electrode for a dye-sensitized solar cell (DSSC), which exhibited 1.65% of power conversion efficiency. To explore broad and practical applications, large-scale synthesis with controllable integration of individual graphene sheets is essential. A novel strategy for the synthesis of graphene sheets with three-dimensional (3D) Honeycomb-like structure has been invented in this project based on a simple and novel chemical reaction (Li2O and CO to graphene and Li2CO3). The simultaneous formation of Li2CO3 with graphene not only can isolate graphene sheets from each other to prevent graphite formation during the process, but also determine the locally curved shape of graphene sheets. After removing Li2CO3, 3D graphene sheets with a honeycomb-like structure were obtained. This would be the first approach to synthesize 3D graphene sheets with a controllable shape. Furthermore, it has been demonstrated that the 3D Honeycomb-Structured Graphene (HSG) possesses excellent electrical conductivity and high catalytic activity. As a result, DSSCs with HSG counter electrodes exhibit energy conversion efficiency as high as 7.8%, which is comparable to that of an expensive noble Pt electrode.

The STEREO/PLASTIC response to solar wind ions (Flight measurements and models)

The Plasma and Supra-Thermal Ion Composition (PLASTIC) instrument is one of four experiment packages on board of the two identical STEREO spacecraft A and B, which were successfully launched from Cape Canaveral on 26 October 2006. During the two years of the nominal STEREO mission, PLASTIC is providing us with the plasma characteristics of protons, alpha particles, and heavy ions. PLASTIC will also provide key diagnostic measurements in the form of the mass and charge state composition of heavy ions. Three measurements (E/qk, time of flight, ESSD) from the pulse height raw data are used to characterize the solar wind ions from the solar wind sector, and part of the suprathermal particles from the wide-angle partition with respect to mass, atomic number and charge state. In this paper, we present a new method for flight data analysis based on simulations of the PLASTIC response to solar wind ions. We present the response of the entrance system / energy analyzer in an analytical form. Based on stopping power theory, we use an analytical expression for the energy loss of the ions when they pass through a thin carbon foil. This allows us to model analytically the response of the time of flight mass spectrometer to solar wind ions. Thus we present a new version of the analytical response of the solid state detectors to solar wind ions. Various important parameters needed for our models were derived, based on calibration data and on the first flight measurements obtained from STEREO-A. We used information from each measured event that is registered in full resolution in the Pulse Height Analysis words and we derived a new algorithm for the analysis of both existing and future data sets of a similar nature which was tested and works well. This algorithm allows us to obtain, for each measured event, the mass, atomic number and charge state in the correct physical units. Finally, an important criterion was developed for filtering our Fe raw flight data set from the pulse height data without discriminating charge states.

Benzo1,2-b:4,5-b 'difuran-based sensitizers for dye-sensitized solar cells

Two BDF-based organic sensitizers, as first examples for their use in dye-sensitized solar cells, are prepared and characterized. They yield promising power conversion efficiencies of up to 5.5 and high open circuit voltages up to 0.82 V. This work demonstrates that the BDF chromophore acts as an effective donor in organic sensitizers.

Relation between Excitation Power Density and Er3+ Doping Yielding the Highest Absolute Upconversion Quantum Yield

The upconversion quantum yield (UCQY) is one of the most significant parameters for upconverter materials. A high UCQY is essential for a succesful integration of upconversion in many applications, such as harvesting of the solar radiation. However, little is known about which doping level of the rare-earth ions yields the highest UCQY in the different host lattices and what are the underlying causes. Here, we investigate which Er3+ doping yields the highest UCQY in the host lattices β-NaYF4 and Gd2O2S under 4I15/2 → 4I13/2 excitation. We show for both host lattices that the optimum Er3+ doping is not fixed and it actually decreases as the irradiance of the excitation increases. To find the optimum Er3+ doping for a given irradiance, we determined the peak position of the internal UCQY as a function of the average Er−Er distance. For this purpose, we used a fit on experimental data, where the average Er−Er distance was calculated from the Er3+ doping of the upconverter samples and the lattice parameters of the host materials. We observe optimum average Er−Er distances for the host lattices β-NaYF4 and Gd2O2S with differences <14% at the same irradiance levels, whereas the optimum Er3+ doping are around 2× higher for β-NaYF4 than for Gd2O2S. Estimations by extrapolation to higher irradiances indicate that the optimum average Er−Er distance converges to values around 0.88 and 0.83 nm for β-NaYF4 and Gd2O2S, respectively. Our findings point to a fundamental relationship and focusing on the average distance between the active rare-earth ions might be a very efficient way to optimize the doping of rare-earth ions with regard to the highest achievable UCQY.

A quinoxaline-fused tetrathiafulvalene-based sensitizer for efficient dye-sensitized solar cells

A new quinoxaline-fused tetrathiafulvalene-based sensitizer has been prepared and characterized. The resulting power conversion efficiency of 6.47% represents the best performance to date for tetrathiafulvalene-sensitized solar cells.

Imaging the Heliosphere using neutral Atoms from Solar Wind Energy down to 15 eV

We study the spatial and temporal distribution of hydrogen energetic neutral atoms (ENAs) from the heliosheath observed with the IBEX-Lo sensor of the Interstellar Boundary EXplorer (IBEX) from solar wind energies down to the lowest available energy (15 eV). All available IBEX-Lo data from 2009 January until 2013 June were included. The sky regions imaged when the spacecraft was outside of Earth's magnetosphere and when the Earth was moving toward the direction of observation offer a sufficient signal-to-noise ratio even at very low energies. We find that the ENA ribbon—a 20° wide region of high ENA intensities—is most prominent at solar wind energies whereas it fades at lower energies. The maximum emission in the ribbon is located near the poles for 2 keV and closer to the ecliptic plane for energies below 1 keV. This shift is an evidence that the ENA ribbon originates from the solar wind. Below 0.1 keV, the ribbon can no longer be identified against the globally distributed ENA signal. The ENA measurements in the downwind direction are affected by magnetospheric contamination below 0.5 keV, but a region of very low ENA intensities can be identified from 0.1 keV to 2 keV. The energy spectra of heliospheric ENAs follow a uniform power law down to 0.1 keV. Below this energy, they seem to become flatter, which is consistent with predictions. Due to the subtraction of local background, the ENA intensities measured with IBEX agree with the upper limit derived from Lyα observations.

The first batteryless, solar-powered cardiac pacemaker

BACKGROUND: Contemporary pacemakers (PMs) are powered by primary batteries with a limited energy-storing capacity. PM replacements because of battery depletion are common and unpleasant and bear the risk of complications. Batteryless PMs that harvest energy inside the body may overcome these limitations. OBJECTIVE: The goal of this study was to develop a batteryless PM powered by a solar module that converts transcutaneous light into electrical energy. METHODS: Ex vivo measurements were performed with solar modules placed under pig skin flaps exposed to different irradiation scenarios (direct sunlight, shade outdoors, and indoors). Subsequently, 2 sunlight-powered PMs featuring a 4.6-cm2 solar module were implanted in vivo in a pig. One prototype, equipped with an energy buffer, was run in darkness for several weeks to simulate a worst-case scenario. RESULTS: Ex vivo, median output power of the solar module was 1963 μW/cm2 (interquartile range [IQR] 1940-2107 μW/cm2) under direct sunlight exposure outdoors, 206 μW/cm2 (IQR 194-233 μW/cm2) in shade outdoors, and 4 μW/cm2 (IQR 3.6-4.3 μW/cm2) indoors (current PMs use approximately 10-20 μW). Median skin flap thickness was 4.8 mm. In vivo, prolonged SOO pacing was performed even with short irradiation periods. Our PM was able to pace continuously at a rate of 125 bpm (3.7 V at 0.6 ms) for 1½ months in darkness. CONCLUSION: Tomorrow's PMs might be batteryless and powered by sunlight. Because of the good skin penetrance of infrared light, a significant amount of energy can be harvested by a subcutaneous solar module even indoors. The use of an energy buffer allows periods of darkness to be overcome.