Efficient Utilization of Solar Energy in Dye-Sensitized Solar Cells and in the Photocatalytic Reduction of Carbon Dioxide

One of the most important questions humanity will face in the next 100 years is going to be What will happen when oil runs out? This dissertation describes efforts to utilize solar energy to improve renewable energy technology in two ways: First, through the improvement of dye sensitized solar cells by theimprovement of D-π-A dye subunits, the development of practical sensitizers, and progress towards stable, tunable redox shuttles. A novel indolizine donor subunit was synthesized that was shown to be the strongest reported donor. Dyes made from this novel donor and devices using the Γ-/I 3- reached up to 5.4% efficiency. This donor was then systematically improved by the addition of non-conjugated substituents, which acted as good surface blocking groups and thus facilitated high performance during device testing. Dyes made using this donor and devices using the Γ-/I 3- redox shuttle reached up to 6.7% efficiency. Second, this thesis describes efforts to close the carbon cycle through utilization of solar energy in CO2 reduction. The described efforts regard the improvement of known catalysts through increased stability and performance, and of the use of a simulated solar spectrum to improve the practicality of photocatalyticCO2 reduction. By the substitution of a pyridyl chelating group for an N-Heterocyclic Carbene (NHC) ligand, the synthesized complexes were more stable while still absorbing visible light. The synthesized complexes operated as photocatalysts with or without a photosensitizer, making this the fourth reported series ofnon-sensitized photocatalysts for CO2 reduction

Intercalation makes the difference with TiS2: Boosting electrocatalytic water oxidation activity through Co intercalation

Intercalated and unmodified TiS2 nanomaterials were synthesized and characterized by UV-Visible-NIR spectroscopy, Powder X-Ray Diffraction, and X-Ray Photoelectron and Ultraviolet Photoelectron Spectroscopy. Photoelectron spectroscopy measurements indicated that CoS and Cu2S appeared to be intercalated between sheets of partially or fully oxidized TiS2, which could be solution processed on conductive oxide substrates. The materials were then applied toward water oxidation and evaluated by cyclic voltammetry, chronoamperometry, and impedance measurements. While unmodified TiS2 was not observed to perform well as an electrocatalyst with overpotentials >3 V in 1 M NaOH electrolyte, CoS intercalation was found to lower the overpotential by ∼1.8-1.44 V at 10 mA/cm2. Conversely, Cu2S intercalation resulted in only a modest increase in performance (>2.3 V overpotential). Impedance measurements indicated that intercalation increased the series resistance in the as-prepared samples but decreased the series resistance in oxidized samples

Photophysics of Deep Blue Acridane- and Benzonitrile-Based Emitter Employing Thermally Activated Delayed Fluorescence

We designed and synthesized a new organic light-emitting diode (OLED) emitter, SBABz4, containing spiro-biacridine donor (D) in the core surrounded by two benzonitrile acceptors (A). The dual A-DxD-A structure is shown to provide pure-blue emission in relation to its single A-D counterpart. Time-resolved photoluminescence (TRPL) recorded in the broad dynamic range from solutions and solid films revealed three emission components: prompt fluorescence, phosphorescence, and efficient thermally activated delayed fluorescence (TADF). The last is independently proven by temperature-dependent TRPL and oxygen-quenching PL experiment. From the PL lifetimes and quantum yield, we estimated maximum external quantum efficiency of 7.1% in SBABz4-based OLEDs and demonstrated 6.8% in a working device

Molecular Engineering of Iridium Blue Emitters Using Aryl N-Heterocyclic Carbene Ligands

The synthesis of a new series of neutral bis[2-(2,4-difluorophen-2-yl)pyridine][1-(2-aryl)-3-methylimidazol-2-ylidene]iridium(III) complexes is reported. Each complex has been characterized by NMR spectroscopy, UV/Vis spectrophotometry, and cyclic voltammetry, and the photophysical properties examined in depth. Furthermore, two of the complexes have been characterized by single-crystal X-ray diffraction analysis. By systematically modifying the cyclometalating aryl group on the N-heterocyclic carbene (NHC) ligand from 2,4-dimethoxyphenyl to 6-methoxy-2-methyl-3-pyridyl, the energy levels of the Ir complexes were modified to produce new blue emitters with increased HOMO and triplet-state energies. OLED devices fabricated with these emitters showed external quantum efficiencies (EQEs) in the range of 2.3-3.2% with low turn-on values of 2.7-2.9 V and efficacies of up to 6.3%

Gradient band structure: high performance perovskite solar cells using poly(bisphenol A anhydride-co-1,3-phenylenediamine)

Surface passivation is a critical factor for improving the photovoltaic performance of perovskite solar cells. However, more robust principle investigations are required to build effective passivation strategies enabling high-performance perovskite solar cells. Here, it is demonstrated that a non-reactive organic polymer induces band-bending at the perovskite surface through a passivation effect, furthermore suppressing Pb(0)formation at the perovskite surface. Consequently, the photovoltaic performance and stability of the perovskite solar cells can be improved. The key findings show that the polymer passivation layer can control the Fermi-level at the perovskite surface, which changes the band structure at the perovskite surface and affects carrier dynamics by suppressing non-radiative pathways. Moreover, the organic polymer can prevent degradation of the perovskite surface. By using the passivating layer, the open circuit voltage improves from 1.046 to 1.100 V, the photoconversion efficiency exceeds 21%, and the stability of the perovskite solar cells is substantially improved. The organic polymer poly(bisphenol A anhydride-co-1,3-phenylenediamine) (PEIm) was used to control the perovskite band structure, and this passivation mechanism is revealed here

Stable perovskite solar cells using tin acetylacetonate based electron transporting layers

Organic-inorganic lead halide perovskites with over 23% power conversion efficiency have attracted enormous academic and industrial attention due to their low-cost fabrication and high device performance. Self-passivated tin oxide as an electron transport layer has shown potential mainly due to the enhanced electron transfer, stability and reduced hysteresis device features. Here we report on novel, non-colloidal tin oxide precursors based on acetylacetonate (one halide free and two halogenated with Cl and Br respectively). We explore the unique film morphology acquired from the non-colloidal precursors and the improved device performance they yield. Our results show that the halide residue in the films plays an impactful role in the thermal durability of the fabricated SnO2 film, as well as providing a passivation layer. Moreover, our optimized tin oxide films achieved an unprecedented power conversion efficiency of 22.19% in planar perovskite solar cells (21.4% certified by Newport), and once upscaled to large-area modules, 16.7% devices based on a 15 cm(2) area were achieved

A Facile Preparative Route of Nanoscale Perovskites over Mesoporous Metal Oxide Films and Their Applications to Photosensitizers and Light Emitters

By two‐step sequential Pb2+ adsorption and reaction with methylammonium‐iodide (MAI) or ‐bromide (MABr) at a low concentration level of 0.06–0.10 m over mesoporous TiO2 or ZrO2 film, a well‐defined nanoscale CH3NH3PbI3 (MAPbI3) photosensitizer or CH3NH3PbBr3 (MAPbBr3) light emitter could be prepared in situ, respectively in a reproducible and atom‐economical way. The as‐prepared nanoscale perovskites are compared with their thin film counterparts in terms of light absorption/emission, crystallinity, surface morphology, and energy‐conversion efficiency. The nanoscale perovskite‐decorated films display more transparency than the bulky film due to the much lower amount deposited, while blueshifted and overwhelmingly brighter photoluminescence is observed in the “nano” relative to the “bulk” due to quantum size confinement. Transmission electron microscopy images also clearly show that a few nanometer‐sized perovskite dots are deposited homogeneously over the surface of TiO2‐ or ZrO2‐particulate film in the course of the current preparative route. When the nano‐MAPbI3 is tested as a photosensitizer in a solid‐state dye‐sensitized solar cell configuration with a very thin (≈650 nm) TiO2 mesoporous film, it has a promising initial power conversion efficiency of 6.23%, which outperformed the result of 2.28% from a typical organic molecular dye coded as MK‐2