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At least 199 records · Page 11

E-beam-enhanced solid-state mechanical amorphization of α-quartz: Reduced deformation barrier via localized excess electrons as network modifiers

Under hydrostatic pressure, α-quartz (α-SiO 2 ) undergoes solid-state mechanical amorphization wherein the interpenetration of [SiO 4 ] 2- tetrahedra occurs and the material loses crystallinity. This phase transformation requires a high hydrostatic pressure of 14GPa because the repulsive forces resulting from the ionic nature of the Si–O bonds prevent the severe distortion of the atomic configuration. Herein, we experimentally and computationally demonstrate that e-beam irradiation changes the nature of the interatomic bonds in α-quartz and enhances the solid-state mechanical amorphization at nanoscale. Specifically, during in situ uniaxial compression, a larger permanent deformation occurs in α-quartz submicron pillars compressed during e-beam irradiation than in those without e-beam irradiation. Microstructural analysis reveals that the large permanent deformation under e-beam irradiation originates from the enhanced mechanical amorphization of α-quartz and the subsequent viscoplastic deformation of the amorphized region. Further, atomic-scale simulations suggest that the delocalized excess electrons introduced by e-beam irradiation move to highly distorted atomic configurations and alleviate the repulsive force, thus reducing the barrier to the solid-state mechanical amorphization. In conclusion, these findings deepen our understanding of electron–matter interactions and can be extended to new glass forming and processing technologies at nano- and microscale.

36 MATERIALS SCIENCE↗

Microstructure and creep properties of cast near-eutectic Al–Ce–Ni alloys

This study investigates the as-cast and aged microstructures, thermal stability, ambient temperature strengthening, and creep resistance of three ternary Al–Ce–Ni alloys (wt%): near-eutectic Al–10Ce–5Ni (with both eutectic and hypoeutectic regions), hypoeutectic Al-7.5Ce-3.75Ni (with numerous primary Al dendrites), and hypereutectic Al-12.5Ce-6.25Ni (with coarse, blocky primary Al3Ni and Al11Ce3 precipitates and some primary Al dendrites). Depending on the alloy composition and local solidification conditions, the following eutectic morphologies are found: (i) coarse Al–Ce eutectic colonies where Al 11 Ce 3 is in the form of “Chinese script”, (ii) intermingled regions of binary Al–Ce and Al–Ni eutectic colonies, with finer Al 3 Ni and Al 11 Ce 3 fibers, (iii) large ternary eutectic colonies, where the binary Al 3 Ni and Al 11 Ce 3 phases are alternating or intertwining within the individual, fine fibers (diameters of ~60–170 nm, depending on solidification rates), and (iv) ternary eutectic zones (between primary Al dendrites), where fine Al 3 Ni and Al 11 Ce 3 build up a 3D-interconnected network. The high volume fraction of intermetallic phases and extremely fine eutectic spacing/fiber diameter both contribute to high ambient strengthening (higher as-cast microhardness than binary Al–Ce or Al–Ni), and also provide enhanced creep resistance at 300 and 350 °C. Additionally, the alloys are coarsening-resistant up to 425 °C for extended periods, with a gradual decrease in microhardness. The alloys aged at 400 °C to 1050 h show fiber fragmentation and coarsening of the resulting particles, with the faster-diffusing Ni driving more rapid coarsening of the Al 3 Ni particles which engulf finer, more stable Al 11 Ce 3 particles. Severe overaging (performed at 590 °C for 24 h) leads to Al 3 Ni and Al 11 Ce 3 spheroids which remain submicron-sized in eutectic colonies, but micron-sized at colony boundary and at Al dendrite-eutectic interface. Creep resistance at 300 °C of overaged Al–10Ce–5Ni remains substantial, consistent with load-transfer based composite strengthening being an important strengthening mechanism in these alloys, making them excellent candidates for replacement of heavier steel or titanium parts operating under stress up to 300 °C.

36 MATERIALS SCIENCE↗

Effect of grain-boundary θ-Al 2 Cu precipitates on tensile and compressive creep properties of cast Al–Cu–Mn–Zr alloys

Tensile and compressive creep tests were performed at 300 °C on high-temperature Al–Cu–Mn–Zr (ACMZ) alloys with 6 wt% Cu (6Cu) and 9 wt% Cu (9Cu) to evaluate the effect on creep properties of micron-size θ-Al 2 Cu intergranular precipitates. For compressive creep, the increased volume fraction of θ-precipitates at grain boundaries (from ~0.7% in 6Cu to ~ 6% in 9Cu) does not affect deformation rates across the investigated stress range of 15–110 MPa, consistent with creep being controlled by submicron θ'-Al 2 Cu precipitates within grains, whose size and fractions are the same in both alloys. In contrast, for tensile creep, 9Cu creeps faster than 6Cu at stresses above 20 MPa, and this difference increases with the stress level. Additionally, this discrepancy between tensile and compressive creep behavior is explained by cavitation during tensile creep, which is favored by higher volume fraction and larger size of intergranular θ precipitates in 9Cu. Conversely, larger precipitates impede cavity linkage resulting in improved creep ductility of 9Cu as compared to 6Cu at 300 °C.

36 MATERIALS SCIENCE↗

Repurposing the θ (Al 2 Cu) phase to simultaneously increase the strength and ductility of an additively manufactured Al–Cu alloy

The Al–Cu–Mn–Zr (ACMZ) cast family of alloys offers unique properties and value propositions for higher strength, higher temperature lightweight components of future vehicles. Earlier research has demonstrated trade-offs in the selection of the alloy chemistry in which an increase in Cu content from 6 up to 9 wt% improves hot tear resistance but lowers ductility. However, a recent study has demonstrated that higher-Cu (9Cu) ACMZ fabricated with laser powder bed fusion additive manufacturing (AM) results in an increase in both ductility and strength when compared to as-aged microstructure of cast 9Cu alloys. The mechanisms of differing mechanical performance of the cast and AM ACMZ alloys are elucidated in the current paper through the utilization of in situ high energy x-ray diffraction (HEXRD) tensile testing wherein lattice strains of different phases are calculated and correlated to their stresses. The ACMZ alloys consisted of theta (θ) and theta prime (θ') phases (both Al 2 Cu in nominal composition) within an aluminum matrix. The larger micron-size θ phase which decorated the grain boundaries in 9Cu ACMZ cast alloys recorded small lattice strains, while the submicron, homogeneously distributed θ phase in the 9Cu ACMZ AM alloy recorded considerably higher lattice strains. The maximum stress reached in the θ phase for the cast 9Cu alloy was found to be ~280 MPa, which was lower than the AM 9Cu alloy which registered a maximum stress of ~1.4 GPa. These measurements indicate that delayed fracture of the finer intermetallic phases simultaneously improves the ductility and strength of AM 9Cu alloy relative to the cast 9Cu alloy, which exhibits early fracture of the larger intermetallic particles.

36 MATERIALS SCIENCE↗

Efficient light-trapping in ultrathin GaAs solar cells using quasi-random photonic crystals

Ultrathin solar cells reduce material usage and allow the use of lower-quality materials thanks to their one order of magnitude smaller thickness than their conventional counterparts. However, efficient photonic light-trapping is required to harvest the incident light efficiently for an otherwise insufficient absorber thickness. Quasi-random photonic crystals are predicted to have high efficient light-trapping while being more robust under angle and thickness variations than simple photonic crystals. In this study, we experimentally demonstrate a light-trapping solution based on quasi-random photonic crystals fabricated by polymer blend lithography. We control the average lattice parameter by modifying the spin-coating speed. We demonstrate an ultrathin GaAs cell of 260 nm with a rear quasi-random pattern with submicron features, and a J sc = 26.4 mA/cm 2 and an efficiency of 22.35% under the global solar spectrum.

14 SOLAR ENERGY↗

Ultrafine-grained Al-Mg-Zr Alloy Processed by Shear-Assisted Extrusion with High Thermal Stability

Shear-assisted processing and extrusion (ShAPE) is used to consolidate Al-4.2Mg-1.6Zr-0.25Si-0.1Fe (wt.%) powders. The extruded alloy exhibits: (i) near-zero porosity; (ii) an attractive combination of tensile yield strength (~220 MPa), ultimate strength (330 MPa) and elongation (>20%); and (iii) excellent thermal stability at 400 ºC. The ultra-fine grain size in the gas-atomized powders – created and stabilized by primary L12-Al3Zr submicron precipitates - is maintained after consolidation and subsequent exposure at 400 ºC, contributing twice as much to strength as Mg in solid-solution. Electron microscopy reveals the microstructure of the L12-Al3Zr precipitates, and other precipitates (Mg2Si and Al3Fe) and dispersoids (oxides).

ShAPE, Friction Extrusion, aluminum powder, Shear ↗

Tribological behavior of hybrid Aluminum-TiB 2 metal matrix composites for brake rotor applications

Here, this research investigates the feasibility of hybrid aluminum metal matrix composites (MMC) incorporating TiB 2 particles for brake rotor applications. The composites were produced by incorporating both in-situ, submicron-sized TiB 2 particles and regular micron-sized TiB 2 powders via stir and squeeze casting techniques into A206 aluminum alloy matrix. Systematic adjustments in the fractions of in-situ and ex-situ TiB 2 particles were conducted to evaluate their impact on wear behavior and mechanisms. Combination of both particle types allowed composites with up to 10 vol% of reinforcements. Composites with higher proportions of ex-situ particles demonstrated increased wear resistance compared to those solely composed of in-situ particles, control specimens without TiB 2 , and conventional cast iron counterparts. The lowest wear rate for the hybrid composites sliding against phenolic brake pads was 1.1 × 10 -5 mm 3 /Nm, signifying a 3-fold reduction relative to cast iron sliding against the same pads. Wear analysis elucidated distinctive mechanisms within the hybrid composites, characterized by mild fragmented abrasive wear, adhesive wear, and plastic deformation, accompanied by the formation of an intermixed tribo-oxide layer.

42 ENGINEERING↗

Reaching the potential of electron diffraction

Microcrystal electron diffraction (MicroED) is an emerging structural technique in which submicron crystals are used to generate diffraction data for structural studies. Structures allow for the study of molecular-level architecture and drive hypotheses about modes of action, mechanisms, dynamics, and interactions with other molecules. Combining cryoelectron microscopy (cryo-EM) instrumentation with crystallographic techniques, MicroED has led to three-dimensional structural models of small molecules, peptides, and proteins and has generated tremendous interest due to its ability to use vanishingly small crystals. In this perspective, we describe the current state of the field for MicroED methodologies, including making and detecting crystals of the appropriate size for the technique, as well as ways to best handle and characterize these crystals. Our perspective provides insight into ways to unlock the full range of potential for MicroED to access previously intractable samples and describes areas of future development.

3D ED↗

Mesoporous Thin Film Architectures: Addressing Material Demands through Molecular Self-Assembly

Mesoporous thin films spark interest across a wide range of disciplines due to their tunable nanostructures, large internal surface areas, and strong compatibility with planar optical, electronic, and microfluidic devices. While attention in the porous materials community has shifted toward macroporous or disordered nanoporous systems, a resurgence in mesoporous thin film research is underway, driven by new molecular self-assembly methods, advanced materials chemistry, and improved characterization techniques. The integration of high-χN block copolymer design, kinetically persistent micelle templating, and postdeposition processing protocols now allows control over structural parameters such as pore size, wall thickness, porosity, and connectivity. These advances have overcome many of the thermodynamic and processing constraints that previously limited widespread adoption. Rather than serving only as high-surface-area supports, mesoporous thin films are engineered as active interfaces where responsive chemistries and nanoscale confinement act in tandem. Embedding switchable ligands, thermoresponsive polymers, redox mediators, or ion-selective groups directly within the pore walls enables real-time control over transport, optical, and electrochemical properties. These capabilities open up new directions in adaptive coatings, gated membranes, and fast-response biosensors. To further expand their functional scope, mesoporous films are integrated into hierarchical and multicomponent architectures. Techniques such as triblock terpolymer templating, crack-directed assembly, and nanoimprint lithography allow for control over spatial organization on the micron and submicron scale and pore system orientation. This enables programmable anisotropy, enhanced molecular diffusion, and wavelength-selective photonic behavior, essential for next-generation sensing, catalysis, and energy applications. Such structural and functional complexity requires equally sophisticated characterization. Multimodal and in situ techniques can track material dynamics under operational conditions. Recent progress includes extended-range ellipsometric porosimetry (EP) for hierarchical architectures, vacuum EP for interface energetics, time-resolved EP for diffusion kinetics, and correlative AFM-SAXS mapping. The introduction of advanced neutron-based spectroscopies, particularly quasielastic neutron scattering (QENS), promises to provide real-time access to ion transport dynamics and segmental motion under nanoscale confinement, offering a path toward deeper mechanistic understanding of structure-performance correlations in mesoporous systems. This Account reflects the technical advances made and the interdisciplinary collaborations that have shaped our collective vision. The particular dimensions of mesopores enable us to subtly tune interactions at the molecular, interfacial, and mesoscopic levels that permit us to harness nanoconfinement. What emerges is a versatile, modular platform capable of chemical gating, energy transduction, and sensing with a level of tunability unmatched by other porous materials. We highlight critical challenges including the need for more robust large-area processing, a deeper understanding of dynamic behavior under cycling, and better integration with device-level architectures. Our strategies support the transition of mesoporous thin films into active high-performance components in next-generation energy, environmental, and biomedical systems.

oxides↗

Broadband Fourier-Transform Optical Photothermal Infrared Spectroscopy and Imaging

Infrared (IR) spectroscopy is a powerful method for mapping chemical heterogeneity on the microscale. Synchrotron IR radiation uniquely provides a high brightness and broad bandwidth to further extend the capabilities of IR spectroscopic imaging. However, the diffraction-limited spatial resolution of IR spectroscopy is insufficient for studies requiring submicrometer spatial differentiation. Optical photothermal IR (O-PTIR) microscopy is a powerful, emerging method that overcomes the IR diffraction limit in IR hyperspectral imaging by employing a modulated IR beam and a visible probe laser beam to detect local temperature-induced modulation at the visible diffraction limit. In this work, we extend the spectral range of photothermal infrared measurements by incorporating a synchrotron IR source, demonstrating a combined synchrotron-based O-PTIR modality that enables high spatial resolution far-field chemical imaging spanning the entire mid-IR range. Both optical- and fluorescence-detected photothermal modalities were performed using a step-scan interferometer, demonstrating improved spectral range (541-4000 cm-1) when compared to optical photothermal microscopy with commercial laser sources (800-1800 cm-1 for this particular source) and improved spatial resolution, when compared to synchrotron microspectroscopy measurements. Following these initial validation studies, synchrotron Fourier-transform fluorescence-detected photothermal IR spectroscopy in combination with synchrotron microspectroscopy measurements was used to differentiate cells in mouse brain tissue sections, which requires submicron spatial resolutions beyond those accessible by IR spectroscopy alone.

Razumtcev, Aleksandr↗

Functionalized Polymer Thin Films for Plutonium Capture and Isotopic Screening from Aqueous Sources

The rapid screening of plutonium from aqueous sources remains a critical challenge for nuclear nonproliferation efforts. The determination of trace-level Pu isotopes in water requires offsite sample preparation and analysis; therefore, new methods that combine plutonium purification, concentration, and isotopic screening in a fieldable detection system will provide an invaluable tool for nuclear safeguards. This contribution describes the development and characterization of thin polymer-ligand films for the isolation and concentration of waterborne Pu for direct spectroscopic analyses. Submicron thin films were prepared through spin coating onto Si wafers and consisted of combinations of polystyrene (PS) with dibenzoylmethane, thenoyltrifluoroacetone, and di(2-ethylhexyl)phosphoric acid (HDEHP). Pu uptake studies from solutions at pH from 2.3 to 6.3 indicated that only films containing HDEHP exhibited significant recovery of Pu. High alpha spectroscopy peak energy resolutions were achieved for PS-HDEHP films over a range of film thicknesses from 30 to 250 nm. Furthermore, a separate study was performed to evaluate uptake from a primarily Pu(V) solution where it was observed that doubling the HDEHP loading in the film increased uptake of Pu by an order of magnitude. X-ray photoelectron spectroscopy (XPS) analysis revealed that HDEHP was highly concentrated within the first few nanometers of the film at the higher loading. XPS analysis also revealed that, in the presence of water, HDEHP was stripped from the surface layer of the film at circumneutral pH. While significant losses of ligand were seen in all samples, higher loadings of HDEHP resulted in measurable amounts of ligand retained after a 12-h soak in water. Findings of this study are being used to guide the development of thin-film composite membrane-based detection methods for the rapid, fieldable analysis of Pu in water.

36 MATERIALS SCIENCE↗

Development of High-Efficiency GaAs Solar Cells Grown on Nanopatterned GaAs Substrates

One approach to reducing the cost of high-efficiency III–V devices involves adding patterned layers to heteroepitaxial or homoepitaxial substrates to facilitate substrate removal and reuse. However, few studies have focused explicitly on high-quality devices grown over patterned substrates, which is required for any cost saving to be beneficial. In this work, we demonstrate the growth of high-efficiency GaAs solar cells on GaAs substrates patterned with an array of nanoscale SiOX mask stripes. We show that reducing the pattern dimensions to submicron length scales with nanoimprint lithography enables defect-free coalescence. By varying the growth conditions, faceting of the epilayer material during overgrowth of the patterned mask was also controlled. A V/III ratio of 200 during MOVPE overgrowth produced smooth coalesced epilayers, which is desirable for the growth of subsequent device layers. Inverted GaAs front homojunction devices grown on patterned GaAs(001) substrates achieved threading dislocation densities below 5 × 10 5 cm –2 and maintained >23% solar cell efficiencies at one sun illumination, equivalent to control devices grown on unpatterned epi-ready substrates.

14 SOLAR ENERGY↗

Response of fs-Laser-Irradiated Diamond by Ultrafast Electron Diffraction

Structural details of the proposed solid–liquid phase transition of carbon have remained elusive, despite years of study. While it is theorized that novel carbon materials form from a liquid precursor, experimental studies have lacked the temporal and spatial resolution necessary to fully characterize the purported liquid state. Here, in this work, we utilize megaelectronvolt-ultrafast electron diffraction (MeV-UED) to study laser irradiated submicron diamond thin films in a pump–probe scheme with picosecond time resolution to visualize potential structural changes of excited diamond. We probe the structure of diamond using a combination of fluences (13, 40 J/cm 2 ) and time delays (10, 25, 100 ps), but observe negligible changes in the static diffraction pattern of diamond and an overall decrease in diffraction intensity up to 100 ps after the excitation pulse. We thus conclude that no appreciable amount of liquid or graphitized carbon is present and highlight the structural resilience of bulk diamond to intense 800 nm ultrafast laser pulses.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

3D Printed Parahydrophobic Surfaces as Multireaction Platforms

We report Parahydrophobic surfaces (PHSs) composed of arrays of cubic μ-pillars with a double scale of roughness and variable wettability were systematically obtained in one step and a widely accessible stereolithographic Formlabs 3D printer. The wettability control was achieved by combining the geometrical parameters (H = height and P = pitch) and the surface modification with fluoroalkyl silane compounds. Homogeneous distribution of F and Si atoms onto the pillars was observed by XPS and SEM-EDAX. A nano-roughness on the heads of the pillars was achieved without any post-treatment. The smallest P values lead to surfaces with static contact angles (CAs) >150° regardless of the H utilized. Interestingly, the relationship 0.6 ≤ H/P ≤ 2.6 obtained here was in good agreement with the H/P values reported for nano- and submicron pillars. Furthermore, experimental CAs, advancing and receding CAs, were consistent with the theoretical prediction from the Cassie–Baxter model. Structures covered with perfluorodecyltriethoxysilane with high H and short P lead to PHSs. Conversely, structures covered with perfluorodecyltrimethoxysilane exhibited a superhydrophobic behavior. Finally, several aqueous reactions, such as precipitation, coordination complex, and nanoparticle synthesis, were carried out by placing the reactive agents as microdroplets on the parahydrophobic pillars, demonstrating the potential application as chemical multi-reaction array platforms for a large variety of relevant fields in microdroplet manipulation, microfluidics systems, and health monitoring, among others.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamic Focusing with High-Quality-Factor Metalenses

Metasurface lenses provide an ultrathin platform in which to focus light, but weak light–matter interactions limit their dynamic tunability. Here we design submicron-thick, ultrahigh quality factor (high-Q) metalenses that enable dynamic modulation of the focal length and intensity. Using full-field simulations, we show that quality factors exceeding 5000 can be generated by including subtle, periodic perturbations within the constituent Si nanoantennas. Such high-Q resonances enable lens modulation based on the nonlinear Kerr effect, with focal lengths varying from 4 to 6.5 μm and focal intensities decreasing by half as input intensity increases from 0.1 to 1 mW/μm 2 . We also show how multiple high-Q resonances can be embedded in the lens response through judicious placement of the perturbations. Our high-Q lens design, with quality factors 2 orders of magnitude higher than existing lens designs, provides a foundation for reconfigurable, multiplexed, and hyperspectral metasurface imaging platforms.

36 MATERIALS SCIENCE↗

Direct Measure of Electrode Spatial Heterogeneity: Influence of Processing Conditions on Anode Architecture and Performance

The spatial (in)homogeneity of aqueous processed silicon electrodes using standard poly(acrylic acid)-based binders and slurry preparation conditions is demonstrated in this work. X-ray nanotomography shows segregation of materials into submicron-thick layers depending on the mixing method and starting binder molecular weights. Using a dispersant, or in situ production of dispersant from the cleavage of the binder into smaller molecular weight species, increases the resulting lateral homogeneity while drastically decreasing the vertical homogeneity as a result of sedimentation and separation due to gravitational forces. This data explains some of the variability in the literature with respect to silicon electrode performance and demonstrates two potential ways to improve slurry-based electrode fabrications.

36 MATERIALS SCIENCE↗

Thermal Conductivity of β-Phase Ga 2 O 3 and (Al x Ga 1– x ) 2 O 3 Heteroepitaxial Thin Films

Heteroepitaxy of β-phase gallium oxide (β-Ga 2 O 3 ) thin films on foreign substrates shows promise for the development of next-generation deep ultraviolet solar blind photodetectors and power electronic devices. In this work, the influences of the film thickness and crystallinity on the thermal conductivity of ($\bar{2}01$)-oriented β-Ga 2 O 3 heteroepitaxial thin films were investigated. Unintentionally doped β-Ga 2 O 3 thin films were grown on c-plane sapphire substrates with off-axis angles of 0° and 6° toward $\langle$$11\bar{2}0$$\rangle$ via metal–organic vapor phase epitaxy (MOVPE) and low-pressure chemical vapor deposition. The surface morphology and crystal quality of the β-Ga 2 O 3 thin films were characterized using scanning electron microscopy, X-ray diffraction, and Raman spectroscopy. The thermal conductivities of the β-Ga 2 O 3 films were measured via time-domain thermoreflectance. The interface quality was studied using scanning transmission electron microscopy. The measured thermal conductivities of the submicron-thick β-Ga 2 O 3 thin films were relatively low as compared to the intrinsic bulk value. The measured thin film thermal conductivities were compared with the Debye–Callaway model incorporating phononic parameters derived from first-principles calculations. The comparison suggests that the reduction in the thin film thermal conductivity can be partially attributed to the enhanced phonon-boundary scattering when the film thickness decreases. They were found to be a strong function of not only the layer thickness but also the film quality, resulting from growth on substrates with different offcut angles. Growth of β-Ga 2 O 3 films on 6° offcut sapphire substrates was found to result in higher crystallinity and thermal conductivity than films grown on on-axis c-plane sapphire. However, the β-Ga 2 O 3 films grown on 6° offcut sapphire exhibit a lower thermal boundary conductance at the β-Ga 2 O 3 /sapphire heterointerface. In addition, the thermal conductivity of MOVPE-grown ($\bar{2}01$)-oriented β-(Al x Ga 1–x ) 2 O 3 thin films with Al compositions ranging from 2% to 43% was characterized. Because of phonon-alloy disorder scattering, the β-(Al x Ga 1–x ) 2 O 3 films exhibit lower thermal conductivities (2.8–4.7 W/m∙K) than the β-Ga 2 O 3 thin films. The dominance of the alloy disorder scattering in β-(Al x Ga 1–x ) 2 O 3 is further evidenced by the weak temperature dependence of the thermal conductivity. This work provides fundamental insight into the physical interactions that govern phonon transport within heteroepitaxially grown β-phase Ga 2 O 3 and (Al x Ga 1–x ) 2 O 3 thin films and lays the groundwork for the thermal modeling and design of β-Ga 2 O 3 electronic and optoelectronic devices.

36 MATERIALS SCIENCE↗

Proton Conducting Silicon Oxide Membranes as a Fluorine Free Alternative to Nafion for Low Temperature Water Electrolysis

Driven by environmental and health concerns related to per- and polyfluoroalkyl substances (PFAS), there has been growing interest in developing fluorine-free proton (H + ) exchange membrane (PEM) materials for fuel cells and water electrolyzers. In this study, we present a side-by-side comparison of the key transport properties of submicron thick, PFAS-free amorphous silicon dioxide (SiO 2 ) membranes to Nafion, a fluorinated polymer electrolyte membrane that represents the industry standard for PEM fuel cells and electrolyzers. Here, measurements of proton (H + ) conductivity (σ H + ), hydrogen (H 2 ) permeability (P H 2 ), and electrical resistivity (ρ e – ) were conducted using model thin films comprised of SiO 2 membranes deposited by atomic layer deposition (ALD). Although the H + conductivity of the SiO 2 membranes is 2–3 orders of magnitude lower than Nafion, the addition of phosphorus dopants (PO x ) improves H + conductivity such that the area specific membrane resistance of thin (<50 nm) PO x -doped SiO 2 membranes is more than an order of magnitude lower than Nafion-117. Importantly, the safe operation of such nanoscale membranes within a PEM electrolyzer is feasible thanks to the low H 2 permeability of dense SiO 2 -based membranes, which are predicted to limit H 2 crossover rates to acceptable levels for pressures up to ≈ 100 bar. As a proof-of-principle demonstration, a chip-scale water electrolyzer based on 100 nm thick PO x -SiO 2 membrane is shown to achieve a current density of 2 A cm –2 at a potential of 2.5 V. If this technology can be successfully scaled up, H + conducting oxide membranes offer an attractive PFAS-free alternative to Nafion for efficient and durable water electrolysis and fuel cell technologies.

Nafion↗