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At least 91 records · Page 5

Anion Exchange Ionomers: Impact of Chemistry on Thin-Film Properties

Ionomer thin-films (i.e., 20–100 nm) on supports serve as model systems to understand ionomer-catalyst interfacial behavior as well as the confinement-driven deviation in properties from bulk membranes. While ionomer thin-films have been examined for proton exchange ionomers, the thin-film properties of anion exchange ionomers (AEIs) remain largely unexplored. More importantly, delineating the convoluted impact of chemistry and confinement on thin-film morphology and hydration is of interest to advancing the field on functional ionic interfaces. In this work, these aspects are studied by using AEIs of different backbones (perfluorinated, aliphatic, and aromatic) and side chains (various lengths, and single versus dual functional groups). Quartz-crystal microbalance and spectroscopic ellipsometry are used to analyze density and coupled with calculated free volume fraction of thin-films to provide insights on their gas transport properties. AEI side-chain's chemical character plays a key role in how confinement modulates hydration (in thin-film versus bulk). Overall, the results elucidate the effects of backbone, side-chain chemistry versus anion/cation type in the confinement-driven changes in thin-film morphology and swelling. This study also provides new insights for tuning AEI transport functionalities at interfaces via chemistry, which can benefit the design and development of electrode-ionomers for alkaline membrane-based energy systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrolyte and Electrode Passivation for Thin Film Batteries

Passivation films for thin film batteries have been prepared and the conductivity and voltage stability window have been measured. Thin films of Li2CO3 have a large voltage stability window of 4.8V, which facilitates the use of this film as a passivation at both the lithium anode-electrolyte interface at high cathodic potentials.

passivation thin film batteries↗

Organic-Inorganic Reaction of Li-Containing thin film: Structure of Lithium Propane Dioxide via MLD

In combining organometallic with organic precursors, molecular layer deposition (MLD) offers not only an expanded portfolio of molecular combinations but specifically the possibility of tuning mechanical properties for more robust functionality. This is appealing for applications in energy storage, where ion transport in and out of electrodes causes significant stress/strain cycling. It is particularly opportune for Li-ion solid state batteries (LISSBs), where electrode and solid electrolyte structures are usually arranged densely for high power and energy. Despite diverse MLD applications to date, little prior research has been aimed at Li-containing MLD materials and processes. Here, we report the MLD growth and process for a lithium-containing organic thin film using lithium tert-butoxide (LiO t Bu) and 1,3-propanediol, leading to an MLD film of lithium propane dioxide, Li 2 O 2 C 3 H 6 (LPDO), identified through X-ray photoelectron spectroscopy (XPS) and ab initio calculations. The growth showed self-limiting behavior for both precursors, with significant nucleation delay before linear growth at 0.23 Å/cycle at 150 °C, and 0.15 Å/cycle at 200 °C. XPS-determined stoichiometry was Li 1.6 O 2.2 C 3 H 6 at both 150 and 200 °C, while additional species, presumably from incomplete reaction, were found at 100 °C, leading to a notably higher (0.84 Å/cycle) growth rate. The LPDO film showed crystallinity and high surface roughness when grown on the crystalline substrate, while on the amorphous substrate, an amorphous LPDO film with low surface roughness was observed. In addition, high air sensitivity of LPDO film was observed, with Li propyl carbonate and Li carbonate formation under air exposure. Further modification strategies were proposed in order to achieve a MLD or atomic layer deposition-/MLD-based solid electrolyte material.

25 ENERGY STORAGE↗

Spray Chemical Vapor Deposition of Single-Source Precursors for Chalcopyrite I-III-VI2 Thin-Film Materials

Thin-film solar cells on flexible, lightweight, space-qualified substrates provide an attractive approach to fabricating solar arrays with high mass-specific power. A polycrystalline chalcopyrite absorber layer is among the new generation of photovoltaic device technologies for thin film solar cells. At NASA Glenn Research Center we have focused on the development of new single-source precursors (SSPs) for deposition of semiconducting chalcopyrite materials onto lightweight, flexible substrates. We describe the syntheses and thermal modulation of SSPs via molecular engineering. Copper indium disulfide and related thin-film materials were deposited via aerosol-assisted chemical vapor deposition using SSPs. Processing and post-processing parameters were varied in order to modify morphology, stoichiometry, crystallography, electrical properties, and optical properties to optimize device quality. Growth at atmospheric pressure in a horizontal hotwall reactor at 395 C yielded the best device films. Placing the susceptor closer to the evaporation zone and flowing a more precursor-rich carrier gas through the reactor yielded shinier-, smoother-, and denser-looking films. Growth of (112)-oriented films yielded more Cu-rich films with fewer secondary phases than growth of (204)/(220)-oriented films. Post-deposition sulfur-vapor annealing enhanced stoichiometry and crystallinity of the films. Photoluminescence studies revealed four major emission bands and a broad band associated with deep defects. The highest device efficiency for an aerosol-assisted chemical vapor deposited cell was one percent.

Hepp, Aloysius F.↗

Evolution of the Rate-Limiting step: From Thin Film to Thick Ni-rich Cathodes

Ni-rich NMC (LiNixMnyCo1-x-yO2, x = 0.6) has the attributes of high specific capacity (greater than 180 mAh g-1), high operating voltage (ca. 3.8 V) and low cost, which is therefore deemed as one of the most promising cathode candidates for next-generation high-energy Li-ion batteries (LIBs). However, challenges exist before the large-scale commercialization of Ni-rich cathode such as gas generation, capacity degradation especially at high rate or elevated temperatures. From thin film to densely pack high loading cathode, this work investigates the rate-limiting steps in Ni-rich cathodes e.g., phase structure, electronic and ionic conductivity to understand the reaction kinetics at different scales. This work provides new insights in understanding the electrochemical properties of Ni-rich cathode at different levels to inspire revolutionary ideas to address the fundamental issues of Ni-rich cathode from materials to relevant electrode levels.

Hu, Jiangtao↗

Reduced recombination via tunable surface fields in perovskite thin films

Here, the ability to reduce energy loss at semiconductor surfaces through passivation or surface field engineering is an essential step in the manufacturing of efficient photovoltaic (PV) and optoelectronic devices. Similarly, surface modification of emerging halide perovskites with quasi-two-dimensional (2D) heterostructures is now ubiquitous to achieve PV power conversion efficiencies (PCEs) >25%, yet a fundamental understanding to how these treatments function is still generally lacking. Here we use a unique combination of depth-sensitive nanoscale characterization techniques to uncover a tunable passivation strategy and mechanism found in perovskite PV devices that were the first to reach the >25% PCE milestone. Namely, treatment with hexylammonium bromide leads to the simultaneous formation of an iodide-rich 2D layer along with a Br halide gradient that extends from defective surfaces and grain boundaries into the bulk three-dimensional (3D) layer. This interface can be optimized to extend the charge carrier lifetime to record values >30 μs and to reduce interfacial recombination velocities to values as low as <7 cm s −1 .

Devices for energy harvesting↗

Doping CdSexTe1-x/CdTe Graded Absorber Films with Arsenic for Thin-Film Photovoltaics

CdTe thin-film photovoltaics have demonstrated some of the lowest costs of electricity generation owing to its low material cost and ease of manufacturing. However, the full potential of polycrystalline CdTe photovoltaics can only be realized if the open-circuit voltage can be increased beyond 1 V Open-circuit voltage ~850-900 mV has been consistently observed for state-of-the-art polycrystalline CdTe solar cells. Open-circuit voltage of over 1V has been demonstrated for single crystal CdTe devices by doping with Group V elements. Therefore, this study is aimed at understanding behavior of polycrystalline CdTe devices with arsenic doping, its activation and process and performance optimization in order to overcome current voltage limitations in CdTe solar cells.

14 SOLAR ENERGY↗

Kinetics and evolution of solid-state metal dealloying in thin films with multimodal analysis

Thin-film solid-state metal dealloying (thin-film SSMD) is an emerging technique that uses self-organization to design nanostructured thin films. The resulting 3D bicontinuous nanostructures are promising for a wide range of applications, such as catalysis and energy storage. In this work, we prepared thin films by SSMD using Ti-Cu as the parent alloy and Mg as the solvent. Using a multimodal approach, we combined synchrotron X-ray spectroscopy, diffraction, and high-resolution electron-based spectroscopy and imaging to study their morphological, structural, and chemical evolution. The processing-structure relationship was analyzed as a function of parent alloy composition and dealloying temperature and time. Morphological transitions from globular, to lamellar, to bicontinuous structures, in conjunction with a ligament size evolution, were identified as functions of the parent alloy composition. The dealloying rate increased with increasing concentration of interdiffusing elements (dissolving component) in the parent alloy. The parting limit, a dealloying compositional threshold, was systematically analyzed and determined to be 30%–40%. The order of crystalline phase formation is CuMg 2 , Cu 2 Mg, and Ti; the Ti phase first shows self-reorganization during dealloying, separate from the crystallization process. The coarsening in thin-film SSMD was identified and not entirely self-similar; in addition to the increase of ligament size over time, the formation of larger globular ligaments were also observed. This work furthers our fundamental understanding of thin-film SSMD and nanostructured thin-film design, where the thermodynamic and kinetic effects differ from the bulk counterparts. The fact that dealloying and diffusion outpaces the crystallization and new phase formation also offers opportunities to utilize thin-film SSMD in certain alloy systems in which deleterious intermetallic phases need to be suppressed, that may not be possible in the bulk geometry.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Metal-ion-controlled growth and nanoindentation response of 3D, bicontinuous Cu–Fe thin films

Bicontinuous, nanocomposite thin film morphologies depend largely on the deposition conditions applied during physical vapor deposition. With the introduction of high power impulse magnetron sputtering (HiPIMS), the range of potential morphologies achieved during deposition has been increased. In this work, we compare the deposition outcomes between traditional direct-current magnetron sputtering (DCMS) and HiPIMS for a thin film co deposit of Cu and Fe. Modular control of the columnarity, porosity and roughness was achieved by varying the Cu and Fe metal ion currents during deposition. The directionality of the nanostructured phase-separated morphology was also controlled as the ion current increased. At zero ion current for both Cu and Fe sputtered species during DCMS, the film exhibited lateral concentration modulations of Cu and Fe. The directionality of the Cu- and Fe-rich phases shifted to vertical concentration modulations at low ion currents of I Fe = 1A and I Cu = 0:1A and to lateral concentration modulations at relatively moderate ion currents of I Fe = 5A and I Cu = 2A: At high ion currents of I Fe = 18A and I Cu = 2A; a more randomized phase domain structure was observed on the nanoscale. This structural shift is rationalized using an interdiffusion model. Here, the role of different kinds of phase separated morphologies, achieved during DCMS deposition, on the mechanical properties has also been studied. Results indicated increase in hardness, indentation modulus and flow strength values with the increase in indentation strain rates. Bicontinuous Cu-Fe nanocomposites are found to be stronger than multilayer Cu-Fe samples.

36 MATERIALS SCIENCE↗

Effect of thickness on metal-to-semiconductor transition in 2-dimensional TiN thin films

Titanium nitride thin films have been grown on c-plane sapphire substrates using a pulsed laser deposition technique in the thickness range of 6–45 nm. X-ray diffraction (XRD) analysis has demonstrated TiN (111) as the preferred orientation of growth on the sapphire substrates. The XRD measurements have also indicated that orientational alignment between the TiN and the sapphire improved with an increase in the TiN film thickness. A change in the resistivity behavior of the TiN thin films from metallic to semiconducting has been observed as the TiN film thickness is reduced below 15 nm. Analyzing and fitting of TiN films’ conductivity data have shown that while the Arrhenius law governs their conductivity in the temperature range of 300–350 K, conductivity values of the films follow the variable range hopping mechanism below 300 K.

36 MATERIALS SCIENCE↗

Local imaging of diamagnetism in proximity-coupled niobium nanoisland arrays on gold thin films.

In this work, we study the effect of engineered disorder on the local magnetic response of proximity-coupled superconducting island arrays by comparing scanning superconducting quantum interference device (SQUID) susceptibility measurements to a model in which we treat the system as a network of one-dimensional (1D) superconductor-normal-metal-superconductor Josephson junctions, each with a Josephson coupling energy E-J determined by the junction length or distance between islands. We find that the disordered arrays exhibit a spatially inhomogeneous diamagnetic response which, for low local applied magnetic fields, is well described by this junction network model, and we discuss these results as they relate to inhomogeneous 2D superconductors. Our model of the static magnetic response of the arrays does not fully capture the onset of nonlinearity and dissipation with increasing applied field, as these effects are associated with vortex motion due to the dynamic nature of the scanning SQUID susceptometry measurement. This work demonstrates a model 2D superconducting system with engineered disorder, and it highlights the impact of dissipation on the local magnetic properties of 2D superconductors and Josephson junction arrays.

Bishop-Van Horn, Logan↗

Thin film temperature sensor

Thin film surface temperature sensors were developed. The sensors were made of platinum-platinum/10 percent rhodium thermocouples with associated thin film-to-lead wire connections and sputtered on aluminum oxide coated simulated turbine blades for testing. Tests included exposure to vibration, low velocity hydrocarbon hot gas flow to 1250 K, and furnace calibrations. Thermal electromotive force was typically two percent below standard type S thermocouples. Mean time to failure was 42 hours at a hot gas flow temperature of 1250 K and an average of 15 cycles to room temperature. Failures were mainly due to separation of the platinum thin film from the aluminum oxide surface. Several techniques to improve the adhesion of the platinum are discussed.

Grant, H. P.↗

Dislocation-Assisted Quasi-Two-Dimensional Semiconducting Nanochannels Embedded in Perovskite Thin Films

Defect engineering in perovskite thin films has attracted extensive attention recently due to the films’ atomic-scale modification, allowing for remarkable flexibility to design novel nanostructures for next generation nanodevices. However, the defect-assisted three-dimensional nanostructures in thin film matrices usually has large misfit strain and thus causes unstable thin film structures. In contrast, defect-assisted one- or two-dimensional nanostructures embedded in thin films can sustain large misfit strains without relaxation, which make them suitable for defect engineering in perovskite thin films. Here, we reported the fabrication and characterization of edge-type misfit dislocation-assisted two-dimensional BiMnO x nanochannels embedded in SrTiO 3 /La 0.7 Sr 0.3 MnO 3 /TbScO 3 perovskite thin films. The nanochannels are epitaxially grown from the surrounding films without noticeable misfit strain. Diode-like current rectification was spatially observed at nanochannels due to the formation of Schottky junctions between BiMnO x nanochannels and conducting La 0.7 Sr 0.3 MnO 3 thin films. Such atomically scaled heterostructures constitute more flexible ultimate functional units for nanoscale electronic devices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗