The conceptual design of an electrostatically- actuated liquid mirror is presented. This design uses mercury as a mirror material because it is liquid at room temperature, exhibits high optical reflectivity and is amenable to electrostatic actuation. We assess the feasibility of controlling the mercury surface through electrostatic control. Finite element analysis is used to simulate the surface profile of the liquid mercury subjected to an electrical bias. Because our design employs segmented partitions that we refer to as Mercury Reflecting Surfaces (MRS), we compare the model predictions to experimental measurements of a prototype MRS element. Our findings lay the groundwork for simulating MRS elements for electrostatic actuation which are relevant to realizing fabrication of liquid mirrors with meter-scale dimensions.
We demonstrate how amino-terminated silane monolayers alter the chemical and energetic composition of the TiO2 surface, which controls the interfacial nucleation, growth and energetics of device-relevant, hybrid perovskite (PVSK) thin films. The surface chemistry and energetics of compact TiO2 thin films are modified with a 3-aminopropyltriethoxysilane (APTES) monolayer that can either weakly coordinate Pb2+ ions (–NH2/free base form) or act as a surrogate organic cation (–NH3+/acid form) at the TiO2/PVSK interface, providing for significant differences in the nucleation free energy for the PVSK active layer as a function of NH3+/NH2 ratio. XPS spectra of amine-modified TiO2 surfaces (N 1s core level) demonstrate that we can achieve NH3+/NH2 ratios of between 3:1 and 1:3 depending upon subsequent acid and base treatment, respectively. Methylammonium lead triiodide (MAPbI3) films are incrementally co-evaporated on TiO2, TiO2/APTES-NH3+ and TiO2/APTES-NH2 interfaces, and the chemical composition, growth dynamics and energetics are systematically investigated using in situ X-ray photoelectron spectroscopy (XPS) and UV photoelectron spectroscopy (UPS). The XPS and UPS results reveal that initial nucleation and subsequent growth of the MAPbI3 PVSK film strongly depends on the chemical functionality of the TiO2 surface. The evaporated films display island-like growth on the bare TiO2 surface, which hinders nucleation of the PVSK phase until ca. 15 nm of precursor material is deposited. Conversely, film growth is more layer-by-layer on the amine-modified TiO2 interfaces, which promote nucleation of the PVSK phase within the first ca. 5 nm of deposition. In addition to vacuum evaporated thin films, we show how these TiO2 surface modifications control the morphology and crystallinity of solution-processed PVSK films based on formamidinium and methylammonium organic cations. These studies elucidate the role of TiO2 surface chemistry on the formation mechanism of hybrid PVSK active layers and the interfacial and bulk energetics, which have significant consequences related to the processing and operation of next-generation optoelectronic device platforms.
Here, we show how the surface free energy of the electron-collecting oxide contact has a very pronounced effect on the nucleation free energy of solution-processed organolead halide perovskite thin films, which influences the crystal size/orientation, band-edge energies, conductivity and, ultimately, the performance of solar cell devices. While a great deal of the research community’s attention has been focused on the perovskite deposition methodology (e.g., starting precursors, annealing conditions, etc.), we demonstrate how the surface free energy of the oxide contact itself can be modified to control morphology and optoelectronic properties of the resulting hybrid perovskite thin films. The surface free energy of high-quality oxide contacts deposited by chemical vapor deposition (CVD) and atomic layer deposition (ALD) is modified by functionalization with a variety of self-assembled monolayers. We explore a number of deposition methodologies (e.g., a variety of single step and sequential step approaches) and their effect on the morphological and electronic properties of the resulting perovskite thin films deposited on these modified oxide contacts. Standard atomic force microscopy (AFM) and its conductive analog (cAFM) show how the oxide surface free energy ultimately affects the nanoscale morphology and charge transport characteristics of these semiconductor films. Photoelectron spectroscopy is used to elucidate the chemical composition (e.g., X-ray photoelectron spectroscopy - XPS), band edge energies (e.g., ultraviolet photoelectron spectroscopy - UPS), and the presence of gap states above the valence band (high sensitivity UPS measurements near the Fermi energy) of the hybrid perovskite materials as a function of the oxide surface free energy.
Polythiophene films can be electrodeposited on modified ITO substrates, textured to increase their active surface area,
doped to enhance charge transport, and then interfaced with C60 thin films to create "planar heterojunction" photovoltaic
devices with power conversion efficiencies up to 1%. Preliminary results indicate that these electrodeposited films (e-P3HT) modified with appropriate ligands can serve as hosts for semi-conducting nanoparticles (CdSe NPs). These NPs
may ultimately extend the device spectral sensitivity into the red and near-IR spectral regions.
The heterojunctions formed between different organic dyes (O/O' heterojunctions), organic dyes with contacting oxide or
metal electrodes (O/I heterojunctions), and semiconductor nanoparticles with organic host polymers and ligands (SC-NP/
O heterojunctions) must be understood and optimized in order to enhance the energy conversion efficiencies of
photovoltaics using these materials as their active components. We have used combinations of UV-photoelectron
spectroscopy, and X-ray photoelectron spectroscopy (UPS/XPS) in the characterization of representative
heterojunctions, and extrapolate these studies to the optimization of new photovoltaic and photoelectrochemical energy
conversion devices.
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