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At least 253 records · Page 14

Linking Perfluorosulfonic Acid Ionomer Chemistry and High-Current Density Performance in Fuel-Cell Electrodes

Transport phenomena are key in controlling the performance of electrochemical energy-conversion technologies and can be highly complex, involving multiple length scales and materials/phases. Material designs optimized for one reactant species transport however may inhibit other transport processes. We explore such trade-offs in the context of polymer-electrolyte fuel-cell electrodes, where ionomer thin films provide the necessary proton conductivity but retard oxygen transport to the Pt reaction site and cause interfacial resistance due to sulfonate/Pt interactions. We examine the electrode overall gas-transport resistance and its components as a function of ionomer content and chemistry. Low-equivalent-weight ionomers allow better dissolved-gas and proton transport due to greater water uptake and low crystallinity but also cause significant interfacial resistance due to the high density of sulfonic acid groups. These effects of equivalent weight are also observed via in situ ionic conductivity and CO displacement measurements. Of critical importance, the results are supported by ex situ ellipsometry and X-ray scattering of model thin-film systems, thereby providing direct linkages and applicability of model studies to probe complex heterogeneous structures. Structural and resultant performance changes in the electrode are shown to occur above a threshold sulfonic-group loading, highlighting the significance of ink-based interactions. Furthermore, our findings and methodologies are applicable to a variety of solid-state energy-conversion devices and material designs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dimensional crossover and band topology evolution in ultrathin semimetallic NiTe 2 films

Nickel ditelluride (NiTe 2 ), a recently discovered Type-II Dirac semimetal with topological Dirac fermions near the Fermi energy, is expected to exhibit strong thickness-mediated electronic tunability and intrinsic two-gap superconductivity in the single-layer limit. Realizing such intriguing phenomena requires the fabrication of ultrathin NiTe 2 films and an understanding of the underlying physics that is still under debate. By conducting experimental band mappings of ultrathin films prepared with molecular beam epitaxy, we reveal spectroscopic evidence for the dimensionality crossover of single-crystalline ultrathin NiTe 2 films as a function of film thickness. As the film thickness increases from one to five layers, the gap in the conical topological surface states closes. Comparisons of experimental to first-principles results also highlight difficulties in fabricating atomically smooth single-layer NiTe 2 films. Our results not only provide further impetus for studying emergent phenomena in NiTe 2 but also underscore the limitations of fabricating NiTe 2 films for device applications.

36 MATERIALS SCIENCE↗

Electromagnetic Properties of Aluminum-based Bilayers for Kinetic Inductance Detectors

The complex conductivity of a superconducting thin film is related to the quasiparticle density, which depends on the physical temperature and can also be modified by external pair breaking with photons and phonons. This relationship forms the underlying operating principle of Kinetic Inductance Detectors (KIDs), where the detection threshold is governed by the superconducting energy gap. We investigate the electromagnetic properties of thin-film aluminum that is proximitized with either a normal metal layer of copper or a superconducting layer with a lower T-C, such as iridium, in order to extend the operating range of KIDs. Using the Usadel equations along with the Nam expressions for complex conductivity, we calculate the density of states and the complex conductivity of the resulting bilayers to understand the dependence of the pair breaking threshold, surface impedance, and intrinsic quality factor of superconducting bilayers on the relative film thicknesses. The calculations and analyses provide theoretical insights in designing aluminum-based bilayer kinetic inductance detectors for detection of microwave photons and athermal phonons at the frequencies well below the pair breaking threshold of a pure aluminum film.

complex conductivity↗

Rapid scalable plasma processing of thin-film Li–La–Zr–O solid-state electrolytes

Solid-state electrolytes, such as lithium lanthanum zirconium oxide (LLZO), show promise as technologies for next-generation high-energy-density batteries, but commercial development has been hindered by a lack of scalable processing methods. Current fabrication methods are costly or require long annealing steps to create dense films. We report an atmospheric pressure blown-arc nitrogen plasma jet process to rapidly form sub-micrometer-thick, dense amorphous LLZO (a-LLZO) films from sol-gel precursors. Films are processed in less than 2 min, an order of magnitude faster than what has previously been reported. We demonstrate 500-nm-thick a-LLZO films processed at 350°C with an ionic conductivity of 2 × 10 −6 S/cm at 30°C and 2 × 10 −3 S/cm at 100°C and a conductance of 19 S at 100°C, the highest conductance of any LLZO phase to date. Here, the films exhibit outstanding smooth surface morphology with low defectivity, advancing atmospheric plasma processing as a scalable processing method for solid-state electrolytes.

25 ENERGY STORAGE↗

Microstructural, optical and electrical properties of CdS thin films grown by spray pyrolysis technique as a function of substrate temperature

In this research, nanocrystalline cadmium sulfide thin films were produced by the spray pyrolysis technique on glass substrates. The effects of substrate temperature in the range 400–550 °C on the structural, morphological, optical, and electrical properties of the thin films were investigated. The thin films have been characterized by investigating their X-ray diffraction, field emission scanning electron microscope (FE-SEM), and optical absorption (UV–Vis) measurements. X-ray analysis revealed that thin films were a polycrystalline structure with the hexagonal phase in all cases and by increasing in substrate temperature, crystallite size decreases, and dislocation density increases. The FE-SEM images showed that the surface of the thin films is uniform, homogeneous and without cracks. The average sizes of the grains are at the range of 210–235 nm. The obtained values for optical band gap have been in the range of 2.18–2.41 eV, where the value of optical band gap for the thin films decreases by increasing substrate temperature. The Urbach energies of the thin films increase as the substrate temperature is increased. When substrate temperature increased from 400 to 550 °C, electrical resistivity increased from 531 to 2817 Ω cm, carrier concentration decreased from 15.96 × 10{sup 14} to 3.71 × 10{sup 14} cm{sup −3}, Hall mobility decreased from 7.37 to 5.98 cm{sup 2}/V s. Hall effect analysis indicated that the thin films exhibited n-type conductivity.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

THz and Mid-Infrared Linear Dichroism in the High Tc Superconductor La2-xSrxCuO4

We measure the rotation of the linear polarization of light that is transmitted through a high Tc superconductor film as a function of sample orientation. We observe a linear dichroism signal over the entire probing range from 2 to 230 meV, which is consistent with anisotropic in-plane conductivity. The La2- xSrxCuO4 thin film sample is epitaxially constrained to be tetragonal, so the symmetry breaking is purely electronic.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Composition Dependent Electrochemical Properties of Earth-Abundant Ternary Nitride Anodes

Growing energy storage demands on lithium-ion batteries necessitate exploration of new electrochemical materials as next-generation battery electrode materials. In this work, we investigate the previously unexplored electrochemical properties of earth-abundant and tunable Zn 1-x Sn 1+x N 2 (x = -0.4 to x = 0.4) thin films, which show high electrical conductivity and high gravimetric capacity for Li insertion. Enhanced cycling performance is achieved compared to previously published end-members Zn 3 N 2 and Sn 3 N 4 , showing decreased irreversible loss and increased total capacity and cycle stability. The average reversible capacity observed is >1050 mAh/g for all compositions and 1220 mAh/g for Zn-poor (x = 0.2) films. Extremely Zn-rich films (x = -0.4) show improved adhesion; however, Zn-rich films undergo a phase transformation on the first cycle. Zn-poor and stoichiometric films do not exhibit significant phase transformations which often plague nitride materials and show no required overpotential at the 0.5 V plateau. Cation composition x is explored as a mechanism for tuning relevant mechanical and electrochemical properties, such as capacity, overpotential, phase transformation, electrical conductivity, and adhesion. The lithiation/delithiation experiments confirm the reversible electrochemical reactions. Without any binding additives, the as-deposited electrodes delaminate resulting in fast capacity degradation. We demonstrate the mechanical nature of this degradation through decreased electrode thinning, resulting in cells with improved cycling stability due to increased mechanical stability. Combining composition and electrochemical analysis, this work demonstrates for the first time composition dependent electrochemical properties for the ternary Zn 1-x Sn 1+x N 2 and proposes earth-abundant ternary nitride anodes for increased reversible capacity and cycling stability.

25 ENERGY STORAGE↗

Double-sided electrodynamic screen films

An electrode film includes a first electrode pattern having a first set of parallel conductive electrodes and a second electrode pattern having a second set of parallel conductive electrodes disposed on a first surface of a transparent film, wherein elements of the first electrode pattern do not cross over elements of the second electrode pattern. A third electrode pattern having a third set of parallel conductive electrodes is disposed on a second surface of the transparent film, wherein the first, second and third sets of parallel conductive electrodes are arranged in an interlaced pattern. The electrode patterns are configured to be connected to respective power sources of electrical power supplying respective waveforms to generate a time-varying electric field pattern above a surface of the electrode film.

Tombs, Thomas Nathaniel↗

Influence of misfit dislocations on ionic conductivity at oxide interfaces

Mismatched complex oxide thin films and heterostructures have gained significant traction for use as electrolytes in intermediate temperature solid oxide fuel cells, wherein interfaces exhibit variation in ionic conductivity as compared to the bulk. Although misfit dislocations present at interfaces in these structures impact ionic conductivity, the fundamental mechanisms responsible for this effect are not well understood. To this end, a kinetic lattice Monte Carlo (KLMC) model was developed to trace oxygen vacancy diffusion at misfit dislocations in SrTiO 3 /BaZrO 3 heterostructures and elucidate the atomistic mechanisms governing ionic diffusion at oxide interfaces. The KLMC model utilized oxygen vacancy migration energy barriers computed using molecular statics. While some interfaces promote oxygen vacancy diffusion, others impede their transport. Fundamental factors such as interface layer chemistry, misfit dislocation structure, and starting and ending sites of migrating ions play a crucial role in oxygen diffusivity. Molecular dynamics (MD) simulations were further performed to support qualitative trends for oxygen vacancy diffusion. Overall, the agreement between KLMC and MD is quite good, though MD tends to predict slightly higher conductivities, perhaps a reflection of nuanced structural relaxations that are not captured by KLMC. The current framework comprising KLMC modeling integrated with molecular statics offers a powerful tool to perform mechanistic studies focused on ionic transport in thin film oxide electrolytes and facilitate their rational design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crystallographic registry in epitaxial V3O5 thin films

Crystallographic orientation plays a central role in determining transport properties in correlated oxides with low-hysteresis metal–insulator transitions. Here, V3O5 thin films were grown on Al2O3 (0001) and their crystallographic registry was evaluated using x-ray diffraction and cross-sectional transmission electron microscopy. θ–2θ measurements show a single out-of-plane orientation defined by the (202) reflection. Azimuthal φ-scans of the V3O5 (310) reflection exhibit twelve discrete maxima over 360°, indicating a finite set of in-plane orientations imposed by the substrate symmetry. High-resolution TEM and fast Fourier transform analysis confirm crystallographic coherence at the film–substrate interface. The electrical conductivity exhibits a metal–insulator transition at TMIT ≈ 423 K with no measurable thermal hysteresis and a total change of ~1.6 orders of magnitude between 300 and 480 K. These results establish crystallographic registry in epitaxial V3O5 thin films and provide a structurally well-defined system for future studies of orientation-dependent transport.\r\nT

36 MATERIALS SCIENCE↗

Freestanding and Flexible Micrometer-Thick PEDOT:PSS Film with High Power Factor

High-efficiency thermoelectric materials are vital for sustainable energy. This work presents a reliable method to fabricate freestanding, flexible micrometer-thick films of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), achieving a power factor of 204 μW m –1 K –2 , 4 orders of magnitude higher than pristine films. Furthermore, this improvement stems from polymer chain realignment and enhanced charge transport via solvent doping, coupled with PSS reduction during post-treatment, which also strengthens film mechanics. Crucially, the freestanding nature ensures transferability, making them ideal for versatile applications. Besides thermoelectrics, these highly conductive, robust, and flexible PEDOT:PSS films provide attractive solutions for organic solar cells, battery electrodes, and flexible electronics.

Conjugated Polymers↗

Electronic nematicity in Sr 2 RuO 4

We have measured the angle-resolved transverse resistivity (ARTR), a sensitive indicator of electronic anisotropy, in high-quality thin films of the unconventional superconductor Sr 2 RuO 4 grown on various substrates. The ARTR signal, heralding the electronic nematicity or a large nematic susceptibility, is present and substantial already at room temperature and grows by an order of magnitude upon cooling down to 4 K. In Sr 2 RuO 4 films deposited on tetragonal substrates the highest-conductivity direction does not coincide with any crystallographic axis. In films deposited on orthorhombic substrates it tends to align with the shorter axis; however, the magnitude of the anisotropy stays the same despite the large lattice distortion. These are strong indications of actual or incipient electronic nematicity in Sr 2 RuO 4 .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Bandgap Engineering of Ga 2 O 3 by MOCVD Through Alloying with Indium

Ga 2 O 3 and In 2 O 3 are vital semiconductors with current and future electronic device applications. Here, we study the alloying of In 2 O 3 and Ga 2 O 3 (IGO) and the associated changes in structure, morphology, band gap, and electrical transport properties. Undoped films of IGO were deposited on sapphire substrates with varying indium (In) percentage from zero to 100% by metal-organic chemical vapor deposition (MOCVD). Some films were annealed in H 2 to induce electrical conductivity. The measurements showed the optical band gap decreased by adding In; this was confirmed by density functional (DFT) calculations, which revealed that the nature of the valence band maximum and conduction band minimum strongly relate to the chemistry and that the band gap drops by adding In. The as-grown films were highly resistive except for pure In 2 O 3 , which possesses p-type conductivity, likely arising from In vacancy-related acceptor states. N-type conductivity was induced in all films after H-anneal. DFT calculations revealed that the presence of In decreases the electron effective mass, which is consistent with the electrical transport measurements that showed higher electron mobility for higher In percentage. The work revealed the successful band gap engineering of IGO and the modification of its band structure while maintaining high-quality films by MOCVD.

36 MATERIALS SCIENCE↗

Gold-tantalum alloy films deposited by high-density-plasma magnetron sputtering

Gold-tantalum alloy films are of interest for biomedical and magnetically-assisted inertial confinement fusion applications. Here, we systematically study the effects of substrate tilt (0°–80°) and negative substrate bias (0–100 V) on properties of ≲3-μm-thick films deposited by high-power impulse magnetron sputtering (HiPIMS) from a Au–Ta alloy target (with 80 at. % of Ta). Results reveal that, for all the substrate bias values studied, an increase in substrate tilt leads to a monotonic decrease in film thickness, density, residual compressive stress, and electrical conductivity. Larger substrate bias favors the formation of a body-centered cubic phase, with films exhibiting lower column tilt and higher density, electrical conductivity, and residual compressive stress. Furthermore, these changes are attributed to metal atom ionization effects, based on the lack of correlation with distributions of landing energies and incident angles of depositing species as calculated by Monte Carlo simulations of ballistic collisions and gas phase atomic transport. By varying substrate tilt and bias in HiPIMS deposition, properties of Au–Ta alloy films can be controlled in a very wide range, including residual stress from –2 to +0.5 GPa, density from 12 to 17 g/cm 3 , and the electrical resistivity from 50 to 4500 μΩ cm, enabling optimum deposition conditions to be selected for specific applications.

36 MATERIALS SCIENCE↗

Growth and Characterization of Epitaxial FeWO 4 Thin Films with Controlled Oxygen Stoichiometry

Here, we report the growth of single-phase epitaxial FeWO 4 thin films, using plasma-assisted molecular beam epitaxy, and investigate structural, optical, and electronic properties. The FeWO 4 films grow in (100) orientation on c-plane sapphire (0001) substrates and exhibit 3 rotational twin variants where FeWO 4 [001] is aligned to sapphire [100] equivalent in-plane directions. X-ray diffraction measurements indicate that the epitaxial FeWO 4 (100) structure is optimized when 80-100 W of rf power is applied to an atomic oxygen source during growth, yielding films with minimal strain and impurity phases or other orientations. In films grown with 120 W of rf power, FeWO 4 crystallites develop inhomogeneous and homogeneous strains and are potentially contaminated with Fe 3+ oxide phase impurities. In films grown with 60 W of rf power, FeWO 4 crystallites do not form fully epitaxial layers. X-ray photoelectron spectroscopy indicates that the structural changes are correlated with the Fe 3+ /Fe 2+ oxidation state ratio increasing from 0.6-1.4 with rf power from 60-120 W. X-ray fluorescence spectroscopy indicates that the Fe/W composition ratio is also increasing from 1.1-1.8 with rf power from 60-120 W. Ultraviolet and visible optical absorption spectra indicate a 1.8 ± 0.1 eV band gap with an additional interband absorption feature at 3.1 ± 0.1 eV in the 80-100 W films, with similar onsets observed in the 60 W films. In the 120 W films, the higher lying transition is shifted to 2.7 ± 0.1 eV due to the Fe 3+ enrichment. Electrical resistivity decreases over 2 orders of magnitude with oxidation from 10 4 -10 5 Ω cm in 60 W films to 120 ± 10 Ω cm in 120 W films. Thermopower measurements show p-type to n-type conductivity conversion when oxidation states shift from Fe 2+ majority in the 100 W films to Fe 3+ majority in the 120 W films. We conclude that electron polaron hopping driven by Fe 3+ is a dominant transport mechanism and a source of n-type conductivity in overoxidized FeWO 4 films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Expanding the Zinc Precursor Toolbox: A Comparative Study of Precursors for Thermal ALD of ZnO Thin Films

Atomic layer deposition (ALD) of zinc oxide (ZnO) has been widely researched using diethyl zinc (DEZ)-based methods. The significant importance of thin films of ZnO as transparent conductive oxides (TCO) in optoelectronic devices and photovoltaics warrants examining alternative Zn precursors for ZnO ALD as potential replacements for the pyrophoric DEZ. In this study, we investigated three alternative Zn precursors: Zn(EEKI)2, Zn(DMP)2, ZnEt(HMDS), in the process development for high-quality ZnO thin films and compared them to DEZ. The ALD processes were studied using in situ spectroscopic ellipsometry. The properties of the ALD ZnO films were characterized using ex situ X-ray photoelectron spectroscopy (XPS), Rutherford backscattering spectrometry and nuclear reaction analysis (RBS/NRA), X-ray diffraction (XRD), atomic force microscopy (AFM), transmission electron microscopy (TEM), and ultraviolet-visible (UV/Vis) spectrophotometry. These measurements confirmed the formation of pure, stoichiometric, and polycrystalline ZnO films using all four Zn precursors. Although the selected precursors are chemically diverse Zn compounds, they all yielded saturating ALD processes and high-quality ZnO thin films at 200 °C. This study highlights the potential benefits of alternative zinc precursors in designing ALD processes for ZnO thin films.

Obenlüneschloß, Jorit↗

Wafer-scale quasi-layered tungstate-doped polypyrrole film with high volumetric capacitance

Layered materials are particularly attractive for supercapacitors because of their unique physical, electrical and chemical properties. In this work, we demonstrate a facile and scalable electrochemical deposition method for wafer-scale synthesis of quasi-layered tungstate-doped polypyrrole films (named TALPy) with controllable thickness and size. The as-prepared TALPy film exhibits a high gravimetric density and excellent volumetric capacitance, exceeding many high-performing carbon- and polymer-based film electrodes. Based on combined results of ex-situ X-ray diffraction (XRD), Raman and X-ray photoelectron spectroscopy (XPS), it is determined that TALPy stores charge through an ion intercalation process accompanied by change in oxidation states of polypyrrole backbone, which is referred as intercalation pseudocapacitance. All these results suggest the great promise of electrochemical deposition as a scalable and controllable bottom-up approach for synthesizing quasi-layered conductive organic-inorganic hybrid films for electrochemical energy storage applications with high volumetric performance.

36 MATERIALS SCIENCE↗

Direct Visualization of Charge Migration in Bilayer Tantalum Oxide Films by Multimodal Imaging

Inspired by biological neuromorphic computing, artificial neural networks based on crossbar arrays of bilayer tantalum oxide memristors have shown to be promising alternatives to conventional complementary metal-oxide-semiconductor (CMOS) architectures. In order to understand the driving mechanism in these oxide systems, tantalum oxide films are resistively switched by conductive atomic force microscopy (C-AFM), and subsequently imaged by kelvin probe force microscopy (KPFM) and spatially resolved time-of-flight secondary ion mass spectrometry (ToF-SIMS). These workflows enable induction and analysis of the resistive switching mechanism as well as control over the resistively switched region of the film. In this work it is shown that the resistive switching mechanism is driven by both current and electric field effects. Reversible oxygen motion is enabled by applying low (<1 V) electric fields, while high electric fields generate irreversible breakdown of the material (>1 V). Fully understanding oxygen motion and electrical effects in bilayer oxide memristor systems is a fundamental step toward the adoption of memristors as a neuromorphic computing technology.

36 MATERIALS SCIENCE↗