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This thesis is dedicated to studies of the excited-state dynamics in organic molecular systems for solar energy conversion by employing time-resolved experimental techniques. Organic photovoltaic (OPV) devices have received significant attention in the past decade and reaching record high power conversion efficiencies (PCE) above 17%. An essential step towards reaching the predicted PCE limit of 25.5% is to develop a comprehensive picture of the photophysical processes, specifically the loss processes, in OPV devices. It is the aim of this thesis to investigate and understand the fate of excited-states in organic electron donor/acceptor systems by ultrafast spectroscopic techniques, specifically, to reveal the interplay between energy and charge transfer processes. The first part deals with the identification of different polymorphs in a diketopyrrolopyrrole-based (DPP) polymer. Applying time-resolved photoluminescence (TRPL) measurements to the polymer dissolved in different solvent mixtures and using multivariate curve resolution (MCR) to deconvolute the ground-state absorption spectra reveals the co-existence of an amorphous (α) and two semi-crystalline (β1 and β2) polymer phases. The OPV device performance is shown to increase by the additional absorption of the β2 phase. The second part compares the efficiency of direct and energy transfer-mediated charge generation in prototypical donor-acceptor dyads that use as the electron donor triangulene derivatives chemically linked to the electron acceptor perylenediimide (PDI) block via oligophenylene spacers of different lengths. Charge generation efficiencies are found to be similar and increase with the donor-acceptor spatial separation. A combination of transient absorption (TA) measurements and computation of the dyad’s excited-state landscape revealed the presence of “optically-dark” excited-states that are populated by ultrafast donor-acceptor energy transfer prior to hole (back) transfer. The last part of the dissertation uses TRPL, TA, and time-delayed collection field (TDCF) measurements alongside MCR analysis to provide a comprehensive analysis of the yield of individual photophysical processes in OPV devices. A systematic methodology is proposed and tested on two all-polymer BHJ devices used as model systems. The experimental findings are supported by successful simulation of the solar cells’ JV characteristics using the spectroscopically-determined kinetic parameters. More generally, this approach can be used to quantify efficiency-limiting processes in other donor-acceptor BHJs.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第23025号 / 理博第4702号 / 新制||理||1674(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)准教授 齊藤 尚平, 教授 依光 英樹, 教授 時任 宣博 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

This dissertation demonstrates that it is possible to create a donor-acceptor system that can transform sunlight into electrons. By using site-directed synthesis, it was possible to create a novel trans-A2B2 porphyrin. In the pursuit of creating a supramolecular system, both the novel (TPA-BT)2ZnP and C60imidazole combined in solution such that the nitrogenous lone pair of C60 imidazole would coordinate axially to the zinc atom in the porphyrin. The conjugates' characterization utilized spectral, electrochemical, and computational techniques. Computational studies revealed in the optimized structure that the HOMO localized on the porphyrin and LUMO centered over the C60imidazole entity. Rehm-Weller calculations showed feasibility of singlet-electron transfer. Femtosecond transient absorption studies documented an efficient photoinduced charge separation in the conjugate. The subsequent work through steady-state and time-resolved transient absorption techniques that photoinduced electron transfer takes place between the synthesized phenylimidazole functionalized bisstyrylBODIPY (BDP(Im)2) and three selected zinc tetrapyrroles. This dyad consisted of BDP(Im)2 and either zinc tetratolylporphyrin (ZnP), zinc-tetra-t-butyl phthalocyanine (ZnPc), or zinc tetra-t-butyl naphthalocyanine (ZnNc) in a solution solvated by σ-dichlorobenzene (DCB). The three dyads (BDP(Im)2:ZnP, BDP(Im)2:ZnPc, and BDP(Im)2:ZnNc) were investigated by spectroscopic, computational, and electrochemical methods. The 1:1 complex of the dyads in optical absorption studies were approximately ~104 M-1 suggesting moderately stable binding. Spectral and electrochemical studies of the dyads used to generate energy level diagrams indicated that PET was thermodynamically unfavorable in BDP(Im)2:ZnP but favorable when the zinc tetrapyrrole is selectively excited dyads—as confirmed in femtosecond transient absorption studies. In the third work, two novel tetrads, consisting of charge stabilizing triphenylamine (TPA) to either bithiophene (BT) or terthiophene (TT) via a covalent linker that is attached to the meso-position of a BODIPY. This BODIPY was further extended by linking it to fulleropyrrolidine via a catechol linker to a modified BODIPY. Computational studies revealed the electronic structures of the tetrads, which rendered the HOMO to be on TPA-BT/TPA-TT moiety, while the HOMO-1 to be on the BODIPY entity and the LUMO to localized to the fulleropyrrolidine. Coupling the results with the electrochemistry, deduced that there is the formation of (TPA-TT).+-BODIPY-C60.- and (TPA-BT).+-BODIPY-C60.- as charge-separated states after the selective excitation of BODIPY in the tetrads. Femtosecond transient absorption studies were conducted in non-polar toluene and polar benzonitrile, and results affirmed photoinduced charge separation in the tetrads.

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Photocatalytic carbon dioxide reduction transforms CO2 to useful chemicals and fuels, reducing CO2 emissions and making fossil fuels more renewable. Due to a lack of earthabundant sensitizers, we want to design new earth-abundant sensitizers to go with the many known carbon dioxide reduction catalysts. Zn(II) dipyrrin complexes strongly absorb visible light, but their excited state properties have not been widely studied. To investigate their photophysical properties, two Zn dipyrrin complexes, with and without heavy atoms, were synthesized and characterized by NMR and mass spectrometry. The photophysical properties of the two complexes were measured in polar and non-polar solvents, particularly fluorescence quantum yield and extinction coefficient. Also, through transient absorption spectroscopy, the triplet state quantum yield of both complexes was measures to determine the effect of solvent polarity and heavy atoms on the triplet state formation.

<p> In recent years, a number of qualitative calculations of various nuclear properties have been undertaken based on a "pairing-plus-quadrupole" force model. The present work involves an extension of the techniques associated with this model and is an investigation of the extent to which it can quantitatively predict properties of the low-lying levels of spherical even-even nuclei.</p> <p> As a particular application, the energies of several of the low-lying levels and the reduced transition probabilities for the first 2+ levels are calculated for the even isotopes of lead.</p> <p> These calculations show in a natural way how collective levels arise, and help to clarify the nature both of these and of the non-collective levels.</p> / Thesis / Doctor of Philosophy (PhD)

<p> In order to gain mechanistic information of photoaddition reactions of 2-cyclohexenones, the additions of 2- and 3-methyl-2-cyclohexenone and 2-cyclohexenone to bicyclo[2.2.1]hepta-2,5-diene have been studied. Substituted 2-cyclohexenone products are obtained in addition to cyclobutane derivatives, and it is proposed that the former adducts arise from diradical intermediates and intramolecular hydrogen shifts. The photo-rearrangement, of 4, 4-dimethyl-2-cyclohexenone, and its photocycloaddition to cyclopentene, was studied in order to identify the enone excited state responsible for cycloaddition. These results, and naphthalene quenching experiments, indicate that all of the additions studied proceed via triplet excited states.</p> / Thesis / Doctor of Philosophy (PhD)

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