Transmission Spectra of Rb 87 atoms near an Optical Nanofiber.

We present measurements of the transmission spectra of 87Rb atoms at 780 nm in the vicinity of a nanofiber. A uniform distribution of fixed atoms around a nanofiber should produce a spectrum that is broadened towards the red due to shifts from the van der Waals potential. If the atoms are free, this also produces an attractive force that accelerates them until they collide with the fiber which depletes the steady-state density of near-surface atoms. It is for this reason that measurements of the van der Waals interaction are sparse. We confirm this by measuring the spectrum cold atoms from a magneto-optical trap around the fiber, revealing a symmetric line shape with nearly the natural linewidth of the transition. When we use an auxiliary 750 nm laser we are able to controllably desorb a steady flux of atoms from the fiber that reside near the surface (less than 50 nm) long enough to feel the van der Walls interaction and produce an asymmetric spectrum. We quantify the spectral asymmetry as a function of 750 nm laser power and find a maximum. Our model, which that takes into account the change in the density distribution, qualitatively explains the observations. In the future this can be used as a tool to more comprehensively study atom-surface interactions.

Self-Assembled InAs/GaAs Quantum Dot Solar Cells

Our work focuses on experimental and theoretical studies aimed at establishing a fundamental understanding of the principal electrical and optical processes governing the operation of quantum dot solar cells (QDSC) and their feasibility for the realization of intermediate band solar cell (IBSC). Uniform performance QD solar cells with high conversion efficiency have been fabricated using carefully calibrated process recipes as the basis of all reliable experimental characterization. The origin for the enhancement of the short circuit current density (Jsc) in QD solar cells was carefully investigated. External quantum efficiency (EQE) measurements were performed as a measure of the below bandgap distribution of transition states. In this work, we found that the incorporation of self-assembled quantum dots (QDs) interrupts the lattice periodicity and introduce a greatly broadened tailing density of states extending from the bandedge towards mid-gap. A below-bandgap density of states (DOS) model with an extended Urbach tail has been developed. In particular, the below-bandgap photocurrent generation has been attributed to transitions via confined energy states and background continuum tailing states. Photoluminescence measurement is used to measure the energy level of the lowest available state and the coupling effect between QD states and background tailing states because it results from a non-equilibrium process. A basic I-V measurement reveals a degradation of the open circuit voltage (Voc) of QD solar cells, which is related to a one sub-bandgap photon absorption process followed by a direct collection of the generated carriers by the external circuit. We have proposed a modified Shockley-Queisser (SQ) model that predicts the degradation of Voc compared with a reference bulk device. Whenever an energy state within the forbidden gap can facilitate additional absorption, it can facilitate recombination as well. If the recombination is non-radiative, it is detrimental to solar cell performance. We have also investigated the QD trapping effects as deep level energy states. Without an efficient carrier extraction pathway, the QDs can indeed function as mobile carriers traps. Since hole energy levels are mostly connected with hole collection under room temperature, the trapping effect is more severe for electrons. We have tried to electron-dope the QDs to exert a repulsive Coulomb force to help improve the carrier collection efficiency. We have experimentally observed a 30% improvement of Jsc for 4e/dot devices compared with 0e/dot devices. Electron-doping helps with better carrier collection efficiency, however, we have also measured a smaller transition probability from valance band to QD states as a direct manifestation of the Pauli Exclusion Principle. The non-linear performance is of particular interest. With the availability of laser with on-resonance and off-resonance excitation energy, we have explored the photocurrent enhancement by a sequential two-photon absorption (2PA) process via the intermediate states. For the first time, we are able to distinguish the nonlinearity effect by 1PA and 2PA process. The observed 2PA current under off-resonant and on-resonant excitation comes from a two-step transition via the tailing states instead of the QD states. However, given the existence of an extended Urbach tail and the small number of photons available for the intermediate states to conduction band transition, the experimental results suggest that with the current material system, the intensity requirement for an observable enhancement of photocurrent via a 2PA process is much higher than what is available from concentrated sun light. In order to realize the IBSC model, a matching transition strength needs to be achieved between valance band to QD states and QD states to conduction band. However, we have experimentally shown that only a negligible amount of signal can be observed at cryogenic temperature via the transition from QD states to conduction band under a broadband IR source excitation. Based on the understanding we have achieved, we found that the existence of the extended tailing density of states together with the large mismatch of the transition strength from VB to QD and from QD to CB, has systematically put into question the feasibility of the IBSC model with QDs.

Applications of Photoinduced Electron Transfer Chemistry: Photoremovable Protecting Groups and Carbon Dioxide Conversion

Traditional organic chemistry has long been dominated by ground state thermal reactions. The alternative to this is excited state chemistry, which uses light to drive chemical transformations. There is considerable interest in using this clean renewable energy source due to concerns surrounding the combustion byproducts associated with the consumption of fossil fuels. The work presented in this text will focus on the use of light (both ultraviolet and visible) for the following quantitative chemical transformations: (1) the release of compounds containing carboxylic acid and alcohol functional groups and (2) the conversion of carbon dioxide into other useable chemicals. Chapters 1-3 will introduce and explore the use of photoremovable protecting groups (PPGs) for the spatiotemporal control of molecular concentrations. Two new PPGs are discussed, the 2,2,2-tribromoethoxy group for the protection of carboxylic acids and the 9-phenyl-9-tritylone group for the protection of alcohols. Fundamental interest in the factors that affect C–X bond breaking has driven the work presented in this text for the release of carboxylic acid substrates. Product analysis from the UV photolysis of 2,2,2-tribromoethyl-(2′-phenylacetate) in various solvents results in the formation of H–atom abstraction products as well as the release of phenylacetic acid. The deprotection of alcohols is realized through the use of UV or visible light photolysis of 9-phenyl-9-tritylone ethers. Central to this study is the use of photoinduced electron transfer chemistry for the generation of ion diradicals capable of undergoing bond-breaking chemistry leading to the release of the alcohol substrates. Chapters 4 and 5 will explore the use of N-heterocyclic carbenes (NHCs) as a catalyst for the photochemical reduction of carbon dioxide. Previous experiments have demonstrated that NHCs can add to CO2 to form stable zwitterionic species known as N-heterocylic-2-carboxylates (NHC–CO2). Work presented in this text illustrate that the stability of these species is highly dependent on solvent polarity, consistent with a lengthening of the imidazolium to carbon dioxide bond (CNHC–CCO2). Furthermore, these adducts interact with excited state electron donors resulting in the generation of ion diradicals capable of converting carbon dioxide into formic acid.

Two-State Thermodynamics of Supercooled Water

Water has been called the “most studied and least understood” of all liquids, and upon supercooling its behavior becomes even more anomalous. One particularly fruitful hypothesis posits a liquid-liquid critical point terminating a line of liquid-liquid phase transitions that lies just beyond the reach of experiment. Underlying this hypothesis is the conjecture that there is a competition between two distinct hydrogen-bonding structures of liquid water, one associated with high density and entropy and the other with low density and entropy. The competition between these structures is hypothesized to lead at very low temperatures to a phase transition between a phase rich in the high-density structure and one rich in the low-density structure. Equations of state based on this conjecture have given an excellent account of the thermodynamic properties of supercooled water. In this thesis, I extend that line of research. I treat supercooled aqueous solutions and anomalous behavior of the thermal conductivity of supercooled water. I also address supercooled water at negative pressures, leading to a framework for a coherent understanding of the thermodynamics of water at low temperatures. I supplement analysis of experimental results with data from the TIP4P/2005 model of water, and include an extensive analysis of the thermodynamics of this model.

DEVELOPMENT OF LI+ AND NA+ CONDUCTING CERAMICS AND CERAMIC STRUCTURES FOR USE IN SOLID STATE BATTERIES

A solid state lithium metal battery based on a lithium garnet material was developed, constructed and tested. Specifically, a porous-dense-porous trilayer structure was fabricated by tape casting, a roll-to-roll technique conducive to high volume manufacturing. The high density and thin center layer (< 20 μm) effectively blocks dendrites even over hundreds of cycles. The microstructured porous layers, serving as electrode supports, are demonstrated to increase the interfacial surface area available to the electrodes and increase cathode loading. Reproducibility of flat, well sintered ceramics was achieved with consistent powderbed lattice parameter and ball milling of powderbed. Together, the resistance of the LLCZN trilayer was measured at an average of 7.6 ohm-cm2 in a symmetric lithium cell, significantly lower than any other reported literature results. Building on these results, a full cell with a lithium metal anode, LLCZN trilayer electrolyte, and LiCoO2 cathode was cycled 100 cycles without decay and an average ASR of 117 ohm-cm2. After cycling, the cell was held at open circuit for 24 hours without any voltage fade, demonstrating the absence of a dendrite or short-circuit of any type. Cost calculations guided the optimization of a trilayer structure predicted that resulting cells will be highly competitive in the marketplace as intrinsically safe lithium batteries with energy densities greater than 300 Wh/kg and 1000 Wh/L for under $100/kWh. Also in the pursuit of solid state batteries, an improved Na+ superionic conductor (NASICON) composition, Na3Zr2Si2PO12, was developed with a conductivity of 1.9x10-3 S/cm. New super-lithiated lithium garnet compositions, Li7.06La3Zr1.94Y0.06O12 and Li7.16La3Zr1.84Y0.16O12, were developed and studied revealing insights about the mechanisms of conductivity in lithium garnets.