Axial Higgs mode detected by quantum pathway interference in RTe3.

The observation of the Higgs boson solidified the standard model of particle physics. However, explanations of anomalies (for example, dark matter) rely on further symmetry breaking, calling for an undiscovered axial Higgs mode1. The Higgs mode was also seen in magnetic, superconducting and charge density wave (CDW) systems2,3. Uncovering the vector properties of a low-energy mode is challenging, and requires going beyond typical spectroscopic or scattering techniques. Here we discover an axial Higgs mode in the CDW system RTe3 using the interference of quantum pathways. In RTe3 (R = La, Gd), the electronic ordering couples bands of equal or different angular momenta4-6. As such, the Raman scattering tensor associated with the Higgs mode contains both symmetric and antisymmetric components, which are excited via two distinct but degenerate pathways. This leads to constructive or destructive interference of these pathways, depending on the choice of the incident and Raman-scattered light polarization. The qualitative behaviour of the Raman spectra is well captured by an appropriate tight-binding model, including an axial Higgs mode. Elucidation of the antisymmetric component is direct evidence that the Higgs mode contains an axial vector representation (that is, a pseudo-angular momentum) and hints that the CDW is unconventional. Thus, we provide a means for measuring quantum properties of collective modes without resorting to extreme experimental conditions.

Real-space visualization of a defect-mediated charge density wave transition.

We study the coupled charge density wave (CDW) and insulator-to-metal transitions in the 2D quantum material 1T-TaS2. By applying in situ cryogenic 4D scanning transmission electron microscopy with in situ electrical resistance measurements, we directly visualize the CDW transition and establish that the transition is mediated by basal dislocations (stacking solitons). We find that dislocations can both nucleate and pin the transition and locally alter the transition temperature Tc by nearly ~75 K. This finding was enabled by the application of unsupervised machine learning to cluster five-dimensional, terabyte scale datasets, which demonstrate a one-to-one correlation between resistance-a global property-and local CDW domain-dislocation dynamics, thereby linking the material microstructure to device properties. This work represents a major step toward defect-engineering of quantum materials, which will become increasingly important as we aim to utilize such materials in real devices.

Two-Dimensional Violet Phosphorus P11: A Large Band Gap Phosphorus Allotrope.

The discovery of novel large band gap two-dimensional (2D) materials with good stability and high carrier mobility will innovate the next generation of electronics and optoelectronics. A new allotrope of 2D violet phosphorus P11 was synthesized via a salt flux method in the presence of bismuth. Millimeter-sized crystals of violet-P11 were collected after removing the salt flux with DI water. From single-crystal X-ray diffraction, the crystal structure of violet-P11 was determined to be in the monoclinic space group C2/c (no. 15) with unit cell parameters of a = 9.166(6) Å, b = 9.121(6) Å, c = 21.803(14)Å, ß = 97.638(17)°, and a unit cell volume of 1807(2) Å3. The structure differences between violet-P11, violet-P21, and fibrous-P21 are discussed. The violet-P11 crystals can be mechanically exfoliated down to a few layers (∼6 nm). Photoluminescence and Raman measurements reveal the thickness-dependent nature of violet-P11, and exfoliated violet-P11 flakes were stable in ambient air for at least 1 h, exhibiting moderate ambient stability. The bulk violet-P11 crystals exhibit excellent stability, being stable in ambient air for many days. The optical band gap of violet-P11 bulk crystals is 2.0(1) eV measured by UV-Vis and electron energy-loss spectroscopy measurements, in agreement with density functional theory calculations which predict that violet-P11 is a direct band gap semiconductor with band gaps of 1.8 and 1.9 eV for bulk and monolayer, respectively, and with a high carrier mobility. This band gap is the largest among the known single-element 2D layered bulk crystals and thus attractive for various optoelectronic devices.

Synergizing Electron and Heat Flows in Photocatalyst for Direct Conversion of Captured CO2.

We report a ternary hybrid photocatalyst architecture with tailored interfaces that boost the utilization of solar energy for photochemical CO2 reduction by synergizing electron and heat flows in the photocatalyst. The photocatalyst comprises cobalt phthalocyanine (CoPc) molecules assembled on multiwalled carbon nanotubes (CNTs) that are decorated with nearly monodispersed cadmium sulfide quantum dots (CdS QDs). The CdS QDs absorb visible light and generate electron-hole pairs. The CNTs rapidly transfer the photogenerated electrons from CdS to CoPc. The CoPc molecules then selectively reduce CO2 to CO. The interfacial dynamics and catalytic behavior are clearly revealed by time-resolved and in situ vibrational spectroscopies. In addition to serving as electron highways, the black body property of the CNT component can create local photothermal heating to activate amine-captured CO2 , namely carbamates, for direct photochemical conversion without additional energy input.

A percolation theory for designing corrosion-resistant alloys.

Iron-chromium and nickel-chromium binary alloys containing sufficient quantities of chromium serve as the prototypical corrosion-resistant metals owing to the presence of a nanometre-thick protective passive oxide film1-8. Should this film be compromised by a scratch or abrasive wear, it reforms with little accompanying metal dissolution, a key criterion for good passive behaviour. This is a principal reason that stainless steels and other chromium-containing alloys are used in critical applications ranging from biomedical implants to nuclear reactor components9,10. Unravelling the compositional dependence of this electrochemical behaviour is a long-standing unanswered question in corrosion science. Herein, we develop a percolation theory of alloy passivation based on two-dimensional to three-dimensional crossover effects that accounts for selective dissolution and the quantity of metal dissolved during the initial stage of passive film formation. We validate this theory both experimentally and by kinetic Monte Carlo simulation. Our results reveal a path forward for the design of corrosion-resistant metallic alloys.

Chemical and Physical Characterization of 3D Printer Aerosol Emissions with and without a Filter Attachment.

Fused filament fabrication three-dimensional (3D) printers have been shown to emit ultrafine particles (UFPs) and volatile organic compounds (VOCs). Previous studies have quantified bulk 3D printer particle and VOC emission rates, as well as described particle chemical composition via ex situ analysis. Here, we present size-resolved aerosol composition measurements from in situ aerosol mass spectrometry and ex situ transmission electron microscopy (TEM). Particles were sampled for in situ analysis during acrylonitrile butadiene styrene (ABS) and polylactic acid (PLA) 3D printing activities and ex situ analysis during ABS printing. We examined the effect of a high-efficiency particulate air filter attachment on ABS emissions and particle chemical composition and demonstrate that filtration was effective in preventing UFP emissions and that particles sampled during filtered prints did not have a high contribution (∼4% vs ∼10%) from aromatic ions in the mass spectrum. Ex situ analysis of particles collected during ABS printing was performed via TEM and electron energy loss spectroscopy, which indicated a high level of sp2 bonding type consistent with polymeric styrene. One 3D print with PLA resulted in an aerosol mass size distribution with a peak at ∼300 nm. Unfiltered ABS prints resulted in particle mass size distributions with peak diameters of ∼100 nm.

Edge Capping of 2D-MXene Sheets with Polyanionic Salts To Mitigate Oxidation in Aqueous Colloidal Suspensions.

MXenes have shown promise in myriad applications, such as energy storage, catalysis, EMI shielding, among many others. However, MXene oxidation in aqueous colloidal suspensions when stored in water at ambient conditions remains a challenge. It is now shown that by simply capping the edges of individual MXene flakes, Ti3 C2 Tz and V2 CTz , by polyanions such as polyphosphates, polysilicates or polyborates, it is possible to quite significantly reduce their propensity for oxidation even when held in aerated water for weeks. This breakthrough resulted from the realization that the edges of MXene sheets are positively charged. It is thus an example of selectively functionalizing the edges differently from the MXene sheet surfaces.

Elucidation of insulin assembly at acidic and neutral pH: Characterization of low molecular weight oligomers.

Deficiency in insulin secretion and function that characterize type 2 diabetes often requires administration of extraneous insulin, leading to injection-site amyloidosis. Insulin aggregation at neutral pH is not well understood. Although oligomer formation is believed to play an important role, insulin oligomers have not been fully characterized yet. Here, we elucidate similarities and differences between in vitro insulin aggregation at acidic and neutral pH for a range of insulin concentrations (2.5-100 µM) by using kinetic thioflavin T fluorescence, circular dichroism, atomic force and electron microscopy imaging. Importantly, we characterize the size distribution of insulin oligomers at different assembly stages by the application of covalent cross-linking and gel electrophoresis. Our results show that at the earliest assembly stage, oligomers comprise up to 40% and 70% of soluble insulin at acidic and neutral pH, respectively. While the highest oligomer order increases with insulin concentration at acidic pH, the opposite tendency is observed at neutral pH, where oligomers up to heptamers are formed in 10 µM insulin. These findings suggest that oligomers may be on- and off-pathway assemblies for insulin at acidic and neutral pH, respectively. Agitation, which is required to induce insulin aggregation at neutral pH, is shown to increase fibril formation rate and fibrillar mass both by an order of magnitude. Insulin incubated under agitated conditions at neutral pH rapidly aggregates into large micrometer-sized aggregates, which may be of physiological relevance and provides insight into injection-site amyloidosis and toxic pulmonary aggregates induced by administration of extraneous insulin.

Real-time observation of local strain effects on nonvolatile ferroelectric memory storage mechanisms.

We use in situ transmission electron microscopy to directly observe, at high temporal and spatial resolution, the interaction of ferroelectric domains and dislocation networks within BiFeO3 thin films. The experimental observations are compared with a phase field model constructed to simulate the dynamics of domains in the presence of dislocations and their resulting strain fields. We demonstrate that a global network of misfit dislocations at the film-substrate interface can act as nucleation sites and slow down domain propagation in the vicinity of the dislocations. Networks of individual threading dislocations emanating from the film-electrode interface play a more dramatic role in pinning domain motion. These dislocations may be responsible for the domain behavior in ferroelectric thin-film devices deviating from conventional Kolmogorov-Avrami-Ishibashi dynamics toward a Nucleation Limited Switching model.

Real-time tracking of structural evolution in 2D MXenes using theory-enhanced machine learning.

In situ Electron Energy Loss Spectroscopy (EELS) combined with Transmission Electron Microscopy (TEM) has traditionally been pivotal for understanding how material processing choices affect local structure and composition. However, the ability to monitor and respond to ultrafast transient changes, now achievable with EELS and TEM, necessitates innovative analytical frameworks. Here, we introduce a machine learning (ML) framework tailored for the real-time assessment and characterization of in operando EELS Spectrum Images (EELS-SI). We focus on 2D MXenes as the sample material system, specifically targeting the understanding and control of their atomic-scale structural transformations that critically influence their electronic and optical properties. This approach requires fewer labeled training data points than typical deep learning classification methods. By integrating computationally generated structures of MXenes and experimental datasets into a unified latent space using Variational Autoencoders (VAE) in a unique training method, our framework accurately predicts structural evolutions at latencies pertinent to closed-loop processing within the TEM. This study presents a critical advancement in enabling automated, on-the-fly synthesis and characterization, significantly enhancing capabilities for materials discovery and the precision engineering of functional materials at the atomic scale.

Giant Anisotropic Magnetoresistance in Few-Layer α-RuCl3 Tunnel Junctions.

The spin-orbit-assisted Mott insulator α-RuCl3 is proximate to the coveted quantum spin liquid (QSL) predicted by the Kitaev model. In the search for the pure Kitaev QSL, reducing the dimensionality of this frustrated magnet by exfoliation has been proposed as a way to enhance magnetic fluctuations and Kitaev interactions. Here, we perform angle-dependent tunneling magnetoresistance (TMR) measurements on ultrathin α-RuCl3 crystals with various layer numbers to probe their magnetic, electronic, and crystal structures. We observe a giant change in resistance, as large as ∼2500%, when the magnetic field rotates either within or out of the α-RuCl3 plane, a manifestation of the strongly anisotropic spin interactions in this material. In combination with scanning transmission electron microscopy, this tunneling anisotropic magnetoresistance (TAMR) reveals that few-layer α-RuCl3 crystals remain in the high-temperature monoclinic phase at low temperatures. It also shows the presence of a zigzag antiferromagnetic order below the critical temperature TN ≃ 14 K, which is twice the one typically observed in bulk samples with rhombohedral stacking. Our work offers valuable insights into the relation between the stacking order and magnetic properties of this material, which helps lay the groundwork for creating and electrically probing exotic magnetic phases such as QSLs via van der Waals engineering.

Diameter-dependent phase selectivity in 1D-confined tungsten phosphides.

Topological materials confined in 1D can transform computing technologies, such as 1D topological semimetals for nanoscale interconnects and 1D topological superconductors for fault-tolerant quantum computing. As such, understanding crystallization of 1D-confined topological materials is critical. Here, we demonstrate 1D template-assisted nanowire synthesis where we observe diameter-dependent phase selectivity for tungsten phosphides. A phase bifurcation occurs to produce tungsten monophosphide and tungsten diphosphide at the cross-over nanowire diameter regime of 35-70 nm. Four-dimensional scanning transmission electron microscopy is used to identify the two phases and to map crystallographic orientations of grains at a few nm resolution. The 1D-confined phase selectivity is attributed to the minimization of the total surface energy, which depends on the nanowire diameter and chemical potentials of precursors. Theoretical calculations are carried out to construct the diameter-dependent phase diagram, which agrees with experimental observations. Our findings suggest a crystallization route to stabilize topological materials confined in 1D.

In operando cryo-STEM of pulse-induced charge density wave switching in TaS2.

The charge density wave material 1T-TaS2 exhibits a pulse-induced insulator-to-metal transition, which shows promise for next-generation electronics such as memristive memory and neuromorphic hardware. However, the rational design of TaS2 devices is hindered by a poor understanding of the switching mechanism, the pulse-induced phase, and the influence of material defects. Here, we operate a 2-terminal TaS2 device within a scanning transmission electron microscope at cryogenic temperature, and directly visualize the changing charge density wave structure with nanoscale spatial resolution and down to 300 µs temporal resolution. We show that the pulse-induced transition is driven by Joule heating, and that the pulse-induced state corresponds to the nearly commensurate and incommensurate charge density wave phases, depending on the applied voltage amplitude. With our in operando cryogenic electron microscopy experiments, we directly correlate the charge density wave structure with the device resistance, and show that dislocations significantly impact device performance. This work resolves fundamental questions of resistive switching in TaS2 devices, critical for engineering reliable and scalable TaS2 electronics.

Efficient electrocatalytic valorization of chlorinated organic water pollutant to ethylene.

Electrochemistry can provide an efficient and sustainable way to treat environmental waters polluted by chlorinated organic compounds. However, the electrochemical valorization of 1,2-dichloroethane (DCA) is currently challenged by the lack of a catalyst that can selectively convert DCA in aqueous solutions into ethylene. Here we report a catalyst comprising cobalt phthalocyanine molecules assembled on multiwalled carbon nanotubes that can electrochemically decompose aqueous DCA with high current and energy efficiencies. Ethylene is produced at high rates with unprecedented ~100% Faradaic efficiency across wide electrode potential and reactant concentration ranges. Kinetic studies and density functional theory calculations reveal that the rate-determining step is the first C-Cl bond breaking, which does not involve protons-a key mechanistic feature that enables cobalt phthalocyanine/carbon nanotube to efficiently catalyse DCA dechlorination and suppress the hydrogen evolution reaction. The nanotubular structure of the catalyst enables us to shape it into a flow-through electrified membrane, which we have used to demonstrate >95% DCA removal from simulated water samples with environmentally relevant DCA and electrolyte concentrations.

Topological Metal MoP Nanowire for Interconnect.

The increasing resistance of copper (Cu) interconnects for decreasing dimensions is a major challenge in continued downscaling of integrated circuits beyond the 7 nm technology node as it leads to unacceptable signal delays and power consumption in computing. The resistivity of Cu increases due to electron scattering at surfaces and grain boundaries at the nanoscale. Topological semimetals, owing to their topologically protected surface states and suppressed electron backscattering, are promising candidates to potentially replace current Cu interconnects. Here, we report the unprecedented resistivity scaling of topological metal molybdenum phosphide (MoP) nanowires, and it is shown that the resistivity values are superior to those of nanoscale Cu interconnects <500 nm2 cross-section areas. The cohesive energy of MoP suggests better stability against electromigration, enabling a barrier-free design . MoP nanowires are more resistant to surface oxidation than the 20 nm thick Cu. The thermal conductivity of MoP is comparable to those of Ru and Co. Most importantly, it is demonstrated that the dimensional scaling of MoP, in terms of line resistance versus total cross-sectional area, is competitive to those of effective Cu with barrier/liner and barrier-less Ru, suggesting MoP is an attractive alternative for the scaling challenge of Cu interconnects.

Emergent layer stacking arrangements in c-axis confined MoTe2.

The layer stacking order in 2D materials strongly affects functional properties and holds promise for next-generation electronic devices. In bulk, octahedral MoTe2 possesses two stacking arrangements, the ferroelectric Weyl semimetal Td phase and the higher-order topological insulator 1T' phase. However, in thin flakes of MoTe2, it is unclear if the layer stacking follows the Td, 1T', or an alternative stacking sequence. Here, we use atomic-resolution scanning transmission electron microscopy to directly visualize the MoTe2 layer stacking. In thin flakes, we observe highly disordered stacking, with nanoscale 1T' and Td domains, as well as alternative stacking arrangements not found in the bulk. We attribute these findings to intrinsic confinement effects on the MoTe2 stacking-dependent free energy. Our results are important for the understanding of exotic physics displayed in MoTe2 flakes. More broadly, this work suggests c-axis confinement as a method to influence layer stacking in other 2D materials.

Termination-Property Coupling via Reversible Oxygen Functionalization of MXenes.

MXenes are a growing family of 2D transition-metal carbides and nitrides, which display excellent performance in myriad of applications. Theoretical calculations suggest that manipulation of the MXene surface termination (such as =O or -F) could strongly alter their functional properties; however, experimental control of the MXene surface termination is still in the developmental stage. Here, we demonstrate that annealing MXenes in an Ar + O2 low-power plasma results in increased =O functionalization with minimal formation of secondary phases. We apply this method to two MXenes, Ti2CT x and Mo2TiC2T x (T x represents the mixed surface termination), and show that in both cases, the increased =O content increases the electrical resistance and decreases the surface transition-metal's electron count. For Mo2TiC2O x , we show that the O content can be reversibly altered through successive vacuum and plasma annealing. This work provides an effective way to tune MXene surface functionalization, which may unlock exciting surface-dependent properties.