High-Performance Hydroxide Exchange Membrane Fuel Cell Comprising an Atomic Layer-Deposited Silver Cathode.

Atomic layer deposition (ALD) is emerging as an efficient tool for the precise manufacture of catalysts, owing to its sophisticated surface tailoring capabilities. To overcome the techno-economic limitations of fuel cell electric vehicles (FCEVs), which are considered suitable alternatives to battery electric vehicles (BEVs), the development of cost-efficient high-performance catalysts is essential. In this study, we successfully fabricated a Pt-free cathode for a hydroxide exchange membrane fuel cell (HEMFC) with excellent oxygen reduction activity under extremely low loading of Ag electrocatalysts using ALD. Microstructural analysis confirmed that the surface modification by ALD-Ag nanoparticles exhibited excellent step coverage characteristics on porous carbon nanotubes (CNTs). An HEMFC comprising a CNT cathode surface-decorated with ALD-Ag nanoparticles delivered a high peak power density of 2154 mW mgAg-1 in an alkaline environment at 65 °C. This study demonstrates the applicability of ALD for the manufacture of highly active low-cost electrocatalysts for high-performance HEMFCs.

Magnetic Weyl Semimetal in K_{2}Mn_{3}(AsO_{4})_{3} with the Minimum Number of Weyl Points.

The "hydrogen atom" of magnetic Weyl semimetals, with the minimum number of Weyl points, has received growing attention recently due to the possible presence of Weyl-related phenomena. Here, we report a nontrivial electronic structure of the ferromagnetic alluaudite-type compound K_{2}Mn_{3}(AsO_{4})_{3}. It exhibits only a pair of Weyl points constrained in the z direction by the twofold rotation symmetry, leading to extremely long Fermi arc surface states. In addition, the study of its low-energy effective model results in the discovery of various topological superconducting states, such as the hydrogen atom of a Weyl superconductor. Our Letter provides a feasible platform to explore the intrinsic properties related to Weyl points, and the related device applications.

Scalable nanoporous carbon films allow line-of-sight 3D atomic layer deposition of Pt: towards a new generation catalyst layer for PEM fuel cells.

Although nanoporous carbons are ubiquitous materials that are used in many clean energy and environmental applications, most are in powder form, thus requiring binders to hold particles together. This results in uncontrolled and complex pathways between particles, potentially exacerbating mass transport issues. To overcome these problems, we have developed an unprecedented binderless, self-supported, nanoporous carbon scaffold (NCS) with tunable and monodisperse pores (5-100+ nm), high surface area (ca. 200-575 m2 g-1), and 3-dimensional scalability (1-150+ cm2, 1-1000 µm thickness). Here, it is shown that NCS85 membranes (85 nm pores) are particularly promising as a host for the homogeneous and efficient 3-D atomic layer deposition (ALD) of Pt nanoparticles, due to the facile penetration of gas phase Pt precursor throughout the homogeneous, low tortuosity internal structure. Furthermore, the high density of surface defects of the as-synthesized NCS promotes uniform Pt nucleation with minimal agglomeration. These advantageous features are key to the rapid oxygen reduction kinetics observed under polymer electrolyte membrane (PEM) fuel cell MEA testing conditions. Cells constructed with an optimal ALD Pt loading of 30 cycles are shown to exhibit a specific activity of ≥0.4 mA cm-2Pt which is exemplary when compared to two commercial catalyst layers with comparable Pt mass loadings and tested under the same conditions. Furthermore, a maximum power density of 1230 mW cm-2 (IR-corrected) is obtained, with the limiting current densities approaching a very respectable 3 A cm-2.

Direct Integration of Strained-Pt Catalysts into Proton-Exchange-Membrane Fuel Cells with Atomic Layer Deposition.

The design and fabrication of lattice-strained platinum catalysts achieved by removing a soluble core from a platinum shell synthesized via atomic layer deposition, is reported. The remarkable catalytic performance for the oxygen reduction reaction (ORR), measured in both half-cell and full-cell configurations, is attributed to the observed lattice strain. By further optimizing the nanoparticle geometry and ionomer/carbon interactions, mass activity close to 0.8 A mgPt -1 @0.9 V iR-free is achievable in the membrane electrode assembly. Nevertheless, active catalysts with high ORR activity do not necessarily lead to high performance in the high-current-density (HCD) region. More attention shall be directed toward HCD performance for enabling high-power-density hydrogen fuel cells.

Condensing water vapor to droplets generates hydrogen peroxide.

It was previously shown [J. K. Lee et al., Proc. Natl. Acad. Sci. U.S.A, 116, 19294-19298 (2019)] that hydrogen peroxide (H2O2) is spontaneously produced in micrometer-sized water droplets (microdroplets), which are generated by atomizing bulk water using nebulization without the application of an external electric field. Here we report that H2O2 is spontaneously produced in water microdroplets formed by dropwise condensation of water vapor on low-temperature substrates. Because peroxide formation is induced by a strong electric field formed at the water-air interface of microdroplets, no catalysts or external electrical bias, as well as precursor chemicals, are necessary. Time-course observations of the H2O2 production in condensate microdroplets showed that H2O2 was generated from microdroplets with sizes typically less than ∼10 µm. The spontaneous production of H2O2 was commonly observed on various different substrates, including silicon, plastic, glass, and metal. Studies with substrates with different surface conditions showed that the nucleation and the growth processes of condensate water microdroplets govern H2O2 generation. We also found that the H2O2 production yield strongly depends on environmental conditions, including relative humidity and substrate temperature. These results show that the production of H2O2 occurs in water microdroplets formed by not only atomizing bulk water but also condensing water vapor, suggesting that spontaneous water oxidation to form H2O2 from water microdroplets is a general phenomenon. These findings provide innovative opportunities for green chemistry at heterogeneous interfaces, self-cleaning of surfaces, and safe and effective disinfection. They also may have important implications for prebiotic chemistry.

Tunable Dielectric and Thermal Properties of Oxide Dielectrics via Substrate Biasing in Plasma-Enhanced Atomic Layer Deposition.

The ability to control the properties of dielectric thin films on demand is of fundamental interest in nanoscale devices. Here, we modulate plasma characteristics at the surface of a substrate to tune both dielectric constant and thermal conductivity of amorphous thin films grown using plasma-enhanced atomic layer deposition. Specifically, we apply a substrate bias ranging from 0 to ∼117 V and demonstrate the systematic tunability of various material parameters of Al2O3. As a function of the substrate bias, we find a nonmonotonical evolution of intrinsic properties, including density, dielectric constant, and thermal conductivity. A key observation is that the maximum values in dielectric constant and effective thermal conductivity emerge at different substrate biases. The impact of density on both thermal conductivity and dielectric constant is further examined using a differential effective medium theory and the Clausius-Mossotti model, respectively. We find that the peak value in the dielectric constant deviates from the Clausius-Mossotti model, indicating the change of oxygen fraction in our thin films as a function of substrate bias. This finding suggests that the increased local strength of plasma sheath not only enhances material density but also controls the dynamics of microstructural defect formation beyond what is possible with conventional approaches. Based on our experimental observations and modeling, we further build a phenomenological relation between dielectric constant and thermal conductivity. Our results pave invaluable avenues for optimizing dielectric thin films at the atomic scale for a wide range of applications in nanoelectronics and energy devices.

Magnetic Semimetals and Quantized Anomalous Hall Effect in EuB_{6}.

Exploration of the novel relationship between magnetic order and topological semimetals has received enormous interest in a wide range of both fundamental and applied research. Here we predict that "soft" ferromagnetic material EuB_{6} can achieve multiple topological semimetal phases by simply tuning the direction of the magnetic moment. Explicitly, EuB_{6} is a topological nodal-line semimetal when the moment is aligned along the [001] direction, and it evolves into a Weyl semimetal with three pairs of Weyl points by rotating the moment to the [111] direction. Interestingly, we identify a composite semimetal phase featuring the coexistence of a nodal line and Weyl points with the moment in the [110] direction. Topological surface states and anomalous Hall conductivity, which are sensitive to the magnetic order, have been computed and are expected to be experimentally observable. Large-Chern-number quantum anomalous Hall effect can be realized in its [111]-oriented quantum-well structures.

Grain-Controlled Gadolinia-Doped Ceria (GDC) Functional Layer for Interface Reaction Enhanced Low-Temperature Solid Oxide Fuel Cells.

In this Research Article, gadolinia-doped ceria (GDC), which is a highly catalyzed oxide ionic conductor, was explored to further improve oxygen surface reaction rates using a grain-controlled layer (GCL) concept. Typically, GDC materials have been used as a cathode functional layer by coating the GDC between the electrode and electrolyte to accelerate the oxygen reduction reaction (ORR). To further improve the oxygen surface kinetics of the GDC cathodic layer, we modified the grain boundary density and crystallinity developed in the GDC layer by adjusting RF power conditions during the sputtering process. This approach revealed that engineered nanograins of GDC thin films directly affected ORR kinetics by catalyzing the oxygen surface reaction rate, significantly enhancing the fuel cell performance. Using this innovative concept, the fuel cells fabricated with a GDC GCL demonstrated a peak power density of 240 mW/cm2 at 450 °C.

Spontaneous generation of hydrogen peroxide from aqueous microdroplets.

We show H2O2 is spontaneously produced from pure water by atomizing bulk water into microdroplets (1 µm to 20 µm in diameter). Production of H2O2, as assayed by H2O2-sensitve fluorescence dye peroxyfluor-1, increased with decreasing microdroplet size. Cleavage of 4-carboxyphenylboronic acid and conversion of phenylboronic acid to phenols in microdroplets further confirmed the generation of H2O2 The generated H2O2 concentration was ∼30 µM (∼1 part per million) as determined by titration with potassium titanium oxalate. Changing the spray gas to O2 or bubbling O2 decreased the yield of H2O2 in microdroplets, indicating that pure water microdroplets directly generate H2O2 without help from O2 either in air surrounding the droplet or dissolved in water. We consider various possible mechanisms for H2O2 formation and report a number of different experiments exploring this issue. We suggest that hydroxyl radical (OH) recombination is the most likely source, in which OH is generated by loss of an electron from OH- at or near the surface of the water microdroplet. This catalyst-free and voltage-free H2O2 production method provides innovative opportunities for green production of hydrogen peroxide.

Electrical Properties of Ultrathin Platinum Films by Plasma-Enhanced Atomic Layer Deposition.

The ability to deposit thin and conformal films has become of great importance because of downscaling of devices. However, because of nucleation difficulty, depositing an electrically stable and thin conformal platinum film on an oxide nucleation layer has proven challenging. By using plasma-enhanced atomic layer deposition (PEALD) and TiO2 as a nucleation layer, we achieved electrically continuous PEALD platinum films down to a thickness of 3.7 nm. Results show that for films as thin as 5.7 nm, the Mayadas-Shatzkes (MS) model for electrical conductivity and the Tellier-Tosser model for temperature coefficient of resistance hold. Although the experimental values start to deviate from the MS model below 5.7 nm because of incomplete Pt coverage, the films still show root mean square electrical stability better than 50 ppm over time, indicating that these films are not only electrically continuous but also sufficiently reliable for use in many practical applications.

Revealing the Bonding Environment of Zn in ALD Zn(O,S) Buffer Layers through X-ray Absorption Spectroscopy.

Zn(O,S) buffer layer electronic configuration is determined by its composition and thickness, tunable through atomic layer deposition. The Zn K and L-edges in the X-ray absorption near edge structure verify ionicity and covalency changes with S content. A high intensity shoulder in the Zn K-edge indicates strong Zn 4s hybridized states and a preferred c-axis orientation. 2-3 nm thick films with low S content show a subdued shoulder showing less contribution from Zn 4s hybridization. A lower energy shift with film thickness suggests a decreasing bandgap. Further, ZnSO4 forms at substrate interfaces, which may be detrimental for device performance.

Topological semimetal in honeycomb lattice LnSI.

Recognized as elementary particles in the standard model, Weyl fermions in condensed matter have received growing attention. However, most of the previously reported Weyl semimetals exhibit rather complicated electronic structures that, in turn, may have raised questions regarding the underlying physics. Here, we report promising topological phases that can be realized in specific honeycomb lattices, including ideal Weyl semimetal structures, 3D strong topological insulators, and nodal-line semimetal configurations. In particular, we highlight a semimetal featuring both Weyl nodes and nodal lines. Guided by this model, we showed that GdSI, the long-perceived ideal Weyl semimetal, has two pairs of Weyl nodes residing at the Fermi level and that LuSI (YSI) is a 3D strong topological insulator with the right-handed helical surface states. Our work provides a mechanism to study topological semimetals and proposes a platform for exploring the physics of Weyl semimetals as well as related device designs.

High-throughput screening of inorganic compounds for the discovery of novel dielectric and optical materials.

Dielectrics are an important class of materials that are ubiquitous in modern electronic applications. Even though their properties are important for the performance of devices, the number of compounds with known dielectric constant is on the order of a few hundred. Here, we use Density Functional Perturbation Theory as a way to screen for the dielectric constant and refractive index of materials in a fast and computationally efficient way. Our results constitute the largest dielectric tensors database to date, containing 1,056 compounds. Details regarding the computational methodology and technical validation are presented along with the format of our publicly available data. In addition, we integrate our dataset with the Materials Project allowing users easy access to material properties. Finally, we explain how our dataset and calculation methodology can be used in the search for novel dielectric compounds.

Direct and continuous strain control of catalysts with tunable battery electrode materials.

We report a method for using battery electrode materials to directly and continuously control the lattice strain of platinum (Pt) catalyst and thus tune its catalytic activity for the oxygen reduction reaction (ORR). Whereas the common approach of using metal overlayers introduces ligand effects in addition to strain, by electrochemically switching between the charging and discharging status of battery electrodes the change in volume can be precisely controlled to induce either compressive or tensile strain on supported catalysts. Lattice compression and tension induced by the lithium cobalt oxide substrate of ~5% were directly observed in individual Pt nanoparticles with aberration-corrected transmission electron microscopy. We observed 90% enhancement or 40% suppression in Pt ORR activity under compression or tension, respectively, which is consistent with theoretical predictions.

Bimetallic Nickel/Ruthenium Catalysts Synthesized by Atomic Layer Deposition for Low-Temperature Direct Methanol Solid Oxide Fuel Cells.

Nickel and ruthenium bimetallic catalysts were heterogeneously synthesized via atomic layer deposition (ALD) for use as the anode of direct methanol solid oxide fuel cells (DMSOFCs) operating in a low-temperature range. The presence of highly dispersed ALD Ru islands over a porous Ni mesh was confirmed, and the Ni/ALD Ru anode microstructure was observed. Fuel cell tests were conducted using Ni-only and Ni/ALD Ru anodes with approximately 350 µm thick gadolinium-doped ceria electrolytes and platinum cathodes. The performance of fuel cells was assessed using pure methanol at operating temperatures of 300-400 °C. Micromorphological changes of the anode after cell operation were investigated, and the content of adsorbed carbon on the anode side of the operated samples was measured. The difference in the maximum power density between samples utilizing Ni/ALD Ru and Pt/ALD Ru, the latter being the best catalyst for direct methanol fuel cells, was observed to be less than 7% at 300 °C and 30% at 350 °C. The improved electrochemical activity of the Ni/ALD Ru anode compared to that of the Ni-only anode, along with the reduction of the number of catalytically active sites due to agglomeration of Ni and carbon formation on the Ni surface as compared to Pt, explains this decent performance.

Plasma-Enhanced Atomic Layer Deposition of SiN-AlN Composites for Ultra Low Wet Etch Rates in Hydrofluoric Acid.

The continued scaling in transistors and memory elements has necessitated the development of atomic layer deposited (ALD) of hydrofluoric acid (HF) etch resistant and electrically insulating films for sidewall spacer processing. Silicon nitride (SiN) has been the prototypical material for this need and extensive work has been conducted into realizing sufficiently lower wet etch rates (WERs) as well as leakage currents to meet industry needs. In this work, we report on the development of plasma-enhanced atomic layer deposition (PEALD) composites of SiN and AlN to minimize WER and leakage current density. In particular, the role of aluminum and the optimum amount of Al contained in the composite structures have been explored. Films with near zero WER in dilute HF and leakage currents density similar to pure PEALD SiN films could be simultaneously realized through composites which incorporate ≥13 at. % Al, with a maximum thermal budget of 350 °C.

ALD Zn(O,S) Thin Films' Interfacial Chemical and Structural Configuration Probed by XAS.

The ability to precisely control interfaces of atomic layer deposited (ALD) zinc oxysulfide (Zn(O,S)) buffer layers to other layers allows precise tuning of solar cell performance. The O K- and S K-edge X-ray absorption near edge structure (XANES) of ∼2-4 nm thin Zn(O,S) films reveals the chemical and structural influences of their interface with ZnO, a common electrode material and diffusion barrier in solar cells. We observe that sulfate formation at oxide/sulfide interfaces is independent of film composition, a result of sulfur diffusion toward interfaces. Leveraging sulfur's diffusivity, we propose an alternative ALD process in which the zinc precursor pulse is bypassed during H2S exposure. Such a process yields similar results to the nanolaminate deposition method and highlights mechanistic differences between ALD sulfides and oxides. By identifying chemical species and structural evolution at sulfide/oxide interfaces, this work provides insights into increasing thin film solar cell efficiencies.

Relating Electronic and Geometric Structure of Atomic Layer Deposited BaTiO3 to its Electrical Properties.

Atomic layer deposition allows the fabrication of BaTiO3 (BTO) ultrathin films with tunable dielectric properties, which is a promising material for electronic and optical technology. Industrial applicability necessitates a better understanding of their atomic structure and corresponding properties. Through the use of element-specific X-ray absorption near edge structure (XANES) analysis, O K-edge of BTO as a function of cation composition and underlying substrate (RuO2 and SiO2) is revealed. By employing density functional theory and multiple scattering simulations, we analyze the distortions in BTO's bonding environment captured by the XANES spectra. The spectral weight shifts to lower energy with increasing Ti content and provides an atomic scale (microscopic) explanation for the increase in leakage current density. Differences in film morphologies in the first few layers near substrate-film interfaces reveal BTO's homogeneous growth on RuO2 and its distorted growth on SiO2. This work links structural changes to BTO thin-film properties and provides insight necessary for optimizing future BTO and other ternary metal oxide-based thin-film devices.

Quantifying Geometric Strain at the PbS QD-TiO2 Anode Interface and Its Effect on Electronic Structures.

Quantum dots (QDs) show promise as the absorber in nanostructured thin film solar cells, but achieving high device efficiencies requires surface treatments to minimize interfacial recombination. In this work, lead sulfide (PbS) QDs are grown on a mesoporous TiO2 film with a crystalline TiO2 surface, versus one coated with an amorphous TiO2 layer by atomic layer deposition (ALD). These mesoporous TiO2 films sensitized with PbS QDs are characterized by X-ray and electron diffraction, as well as X-ray absorption spectroscopy (XAS) in order to link XAS features with structural distortions in the PbS QDs. The XAS features are further analyzed with quantum simulations to probe the geometric and electronic structure of the PbS QD-TiO2 interface. We show that the anatase TiO2 surface structure induces PbS bond angle distortions, which increases the energy gap of the PbS QDs at the interface.

The Use of Contact Mode Atomic Force Microscopy in Aqueous Medium for Structural Analysis of Spinach Photosynthetic Complexes.

To investigate the dynamics of photosynthetic pigment-protein complexes in vascular plants at high resolution in an aqueous environment, membrane-protruding oxygen-evolving complexes (OECs) associated with photosystem II (PSII) on spinach (Spinacia oleracea) grana membranes were examined using contact mode atomic force microscopy. This study represents, to our knowledge, the first use of atomic force microscopy to distinguish the putative large extrinsic loop of Photosystem II CP47 reaction center protein (CP47) from the putative oxygen-evolving enhancer proteins 1, 2, and 3 (PsbO, PsbP, and PsbQ) and large extrinsic loop of Photosystem II CP43 reaction center protein (CP43) in the PSII-OEC extrinsic domains of grana membranes under conditions resulting in the disordered arrangement of PSII-OEC particles. Moreover, we observed uncharacterized membrane particles that, based on their physical characteristics and electrophoretic analysis of the polypeptides associated with the grana samples, are hypothesized to be a domain of photosystem I that protrudes from the stromal face of single thylakoid bilayers. Our results are interpreted in the context of the results of others that were obtained using cryo-electron microscopy (and single particle analysis), negative staining and freeze-fracture electron microscopy, as well as previous atomic force microscopy studies.