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At least 163 records · Page 9

Single layer graphene protective layer on GaAs photocathodes for spin-polarized electron source

GaAs-based photocathodes are the primary choice for polarized electron sources, commonly used in polarized electron microscopes and polarized positron sources. GaAs photocathodes are typically activated with cesium and oxygen, which are highly reactive and require an ultra-high vacuum (⁠~ 10 -11 Torr or lower) to operate reliably, resulting in substantial operational difficulties. A short exposure to a mediocre vacuum results in an instantaneous loss of cathode quantum efficiency (QE) due to the chemical reaction of the active layer with residual gas molecules or back-bombardment ions during operation. Covering the GaAs cathode with a 2D material, such as monolayer graphene, could provide protection against such damage due to the inhibition of chemical reactions with residual gas molecules. In this paper, we have incorporated a method known as intercalation to pass the active material underneath the graphene and activate the superlattice GaAs/GaAsP (SL-GaAs) photocathode. X-ray photoelectron spectroscopy, low-energy electron microscopy, and Mott scattering measurements were performed to evaluate the formation of the photocathode under graphene, as well as its spectral response and electron spin polarization. Our results demonstrate that the successful activation of the SL-GaAs photocathode with a graphene protection layer is achieved with a moderate QE. Furthermore, we found that the electron spin polarization of the cathode with a surface protection layer is higher than the conventional cathode without a protection layer.

2D materials↗

Unconventional non-local relaxation dynamics in a twisted trilayer graphene moiré superlattice

Abstract The electronic and structural properties of atomically thin materials can be controllably tuned by assembling them with an interlayer twist. During this process, constituent layers spontaneously rearrange themselves in search of a lowest energy configuration. Such relaxation phenomena can lead to unexpected and novel material properties. Here, we study twisted double trilayer graphene (TDTG) using nano-optical and tunneling spectroscopy tools. We reveal a surprising optical and electronic contrast, as well as a stacking energy imbalance emerging between the moiré domains. We attribute this contrast to an unconventional form of lattice relaxation in which an entire graphene layer spontaneously shifts position during assembly, resulting in domains of ABABAB and BCBACA stacking. We analyze the energetics of this transition and demonstrate that it is the result of a non-local relaxation process, in which an energy gain in one domain of the moiré lattice is paid for by a relaxation that occurs in the other.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Engineering correlated insulators in bilayer graphene with a remote Coulomb superlattice

Electron superlattices allow the engineering of correlated and topological quantum phenomena. The recent emergence of moiré superlattices in two-dimensional heterostructures has led to exciting discoveries related to quantum phenomena. However, the requirement for the moiré pattern poses stringent limitations, and its potential cannot be switched on and off. Here, in this study, we demonstrate remote engineering and on/off switching of correlated states in bilayer graphene. Employing a remote Coulomb superlattice realized by localized electrons in twisted bilayer WS 2 , we impose a Coulomb superlattice in the bilayer graphene with period and strength determined by the twisted bilayer WS 2 . When the remote superlattice is turned off, the two-dimensional electron gas in the bilayer graphene is described by a Fermi liquid. When it is turned on, correlated insulating states at both integer and fractional filling factors emerge. This approach enables in situ control of correlated quantum phenomena in two-dimensional materials hosting a two-dimensional electron gas.

36 MATERIALS SCIENCE↗

H Energetics on Charged Graphene

These data include energy barriers for hydrogen adsorption and desorption on charged graphene, as well as the density of states for hydrogen-decorated graphene layers. Together, they highlight the role of applied charge and electronic doping on hydrogen chemisorption on graphene.

08 HYDROGEN↗

Hetero-Orbital Two-Component Fractional Quantum Hall States in Bilayer Graphene

A two-dimensional electron system exposed to a strong magnetic field produces a plethora of strongly interacting fractional quantum Hall (FQH) states, the complex topological orders of which are revealed through exotic emergent particles, such as composite fermions, and fractionally charged Abelian and non-Abelian anyons. Much insight has been gained by the study of multicomponent FQH states, where spin and pseudospin indices of the electron contribute additional correlation. Traditional multicomponent FQH states develop in situations where the components share the same orbital states and the resulting interactions are pseudospin independent; this homo-orbital nature is also crucial to their theoretical understanding. Here, we study “hetero-orbital” two-component FQH states, in which the orbital index is part of the pseudospin, rendering the multicomponent interactions strongly SU(2) anisotropic in the pseudospin space. Such states, obtained in bilayer graphene at the isospin transition between 𝑁 = 0 and 𝑁 = 1 electron Landau levels, are markedly different from previous homo-orbital two-component FQH states. In particular, we observe strikingly different behaviors for the parallel-vortex and reverse-vortex attachment composite fermion states, and an anomalously strong two-component 2/5 state over a wide range of magnetic field before it abruptly disappears at a high field. Our findings, combined with detailed theoretical calculations, reveal the surprising robustness of the hetero-orbital FQH effects, significantly enriching our understanding of FQH physics in this novel regime.

Bilayer graphene↗

Hydrodynamic thermoelectric transport in Corbino geometry

We study hydrodynamic electron transport in Corbino graphene devices. Due to the irrotational character of the flow, the forces exerted on the electron liquid are expelled from the bulk. We show that in the absence of Galilean invariance, force expulsion produces qualitatively new features in thermoelectric transport: (i) it results in drops of both voltage and temperature at the system boundaries and (ii) in conductance measurements in pristine systems, the electric field is not expelled from the bulk. We obtain thermoelectric coefficients of the system in the entire crossover region between charge neutrality and high electron density regime. The thermal conductance exhibits a sensitive Lorentzian dependence on the electron density. The width of the Lorentzian is determined by the fluid viscosity. Furthermore, this enables determination of the viscosity of electron liquid near charge neutrality from purely thermal transport measurements. In general, the thermoelectric response is anomalous: It violates the Matthiessen's rule, the Wiedemann-Franz law, and the Mott relation.

36 MATERIALS SCIENCE↗

Dynamical Correlations and Order in Magic-Angle Twisted Bilayer Graphene

The interplay of dynamical correlations and electronic ordering is pivotal in shaping phase diagrams of correlated quantum materials. In magic-angle twisted bilayer graphene, transport, thermodynamic, and spectroscopic experiments pinpoint a competition between distinct low-energy states with and without electronic order, as well as between localized and delocalized charge carriers. In this study, we utilize dynamical mean-field theory on the topological heavy fermion model of twisted bilayer graphene to investigate the emergence of electronic correlations and long-range order in the absence of strain. We contrast moment formation, Kondo screening, and ordering on a temperature basis and explain the nature of emergent correlated states based on three central phenomena: (i) the formation of local spin and valley isospin moments around 100 K, (ii) the ordering of the local isospin moments around 10 K preempting Kondo screening, and (iii) a cascadic redistribution of charge between localized and delocalized electronic states upon doping. At integer fillings, we find that low-energy spectral weight is depleted in the symmetric phase, while we find insulating states with gaps enhanced by exchange coupling in the zero-strain ordered phases. Doping away from integer filling results in distinct metallic states: a “bad metal” above the ordering temperature, where scattering off the disordered local moments suppresses electronic coherence, and a “good metal” in the ordered states with coherence of quasiparticles facilitated by isospin order. This finding reveals coherence from order as the microscopic mechanism behind the Pomeranchuk effect observed experimentally by Rozen [] and by Saito []. Upon doping, there is a periodic charge reshuffling between localized and delocalized electronic orbitals leading to cascades of doping-induced Lifshitz transitions, local spectral weight redistributions, and periodic variations of the electronic compressibility ranging from nearly incompressible to negative. Our findings highlight the essential role of charge transfer, hybridization, and ordering in shaping the electronic excitations and thermodynamic properties in twisted bilayer graphene and provide a unified understanding of the most puzzling aspects of scanning tunneling spectroscopy, transport, and compressibility experiments. Published by the American Physical Society 2024

Physics↗

EELS Studies of Cerium Electrolyte Reveal Substantial Solute Concentration Effects in Graphene Liquid Cells

Graphene liquid cell transmission electron microscopy is a powerful technique to visualize nanoscale dynamics and transformations at atomic resolution. However, the solution in liquid cells is known to be affected by radiolysis, and the stochastic formation of graphene liquid cells raises questions about the solution chemistry in individual pockets. In this study, electron energy loss spectroscopy (EELS) was used to evaluate a model encapsulated solution, aqueous CeCl 3 . First, the ratio between the O K-edge and Ce M-edge was used to approximate the concentration of cerium salt in the graphene liquid cell. It was determined that the ratio between oxygen and cerium was orders of magnitude lower than what is expected for a dilute solution, indicating that the encapsulated solution is highly concentrated. To probe how this affects the chemistry within graphene liquid cells, the oxidation of Ce 3+ was measured using time-resolved parallel EELS. Here, it was determined that Ce 3+ oxidizes faster under high electron fluxes, but reaches the same steady-state Ce 4+ concentration regardless of flux. The time-resolved concentration profiles enabled direct comparison to radiolysis models, which indicate rate constants and g-values of certain molecular species are substantially different in the highly concentrated environment. Finally, electron flux-dependent gold nanocrystal etching trajectories showed that gold nanocrystals etch faster at higher electron fluxes, correlating well with the Ce 3+ oxidation kinetics. Understanding the effects of the highly concentrated solution in graphene liquid cells will provide new insight on previous studies and may open up opportunities to systematically study systems in highly concentrated solutions at high resolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrocatalytic Isoxazoline–Nanocarbon Metal Complexes

In this work, we report the synthesis of new carbon-nanomaterial-based metal chelates that enable effective electronic coupling to electrocatalytic transition metals. In particular, multiwalled carbon nanotubes (MWCNTs) and few-layered graphene (FLG) were covalently functionalized by a microwave-assisted cyclo-addition with nitrile oxides to form metal-binding isoxazoline functional groups with high densities. The covalent attachment was evidenced by Raman spectroscopy, and the chemical identity of the surface functional groups was confirmed by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The functional carbon nanomaterials effectively chelate precious metals Ir(III), Pt(II), and Ru(III), as well as earth-abundant metals such as Ni(II), to afford materials with metal contents as high as 3.0 atom %. The molecularly dispersed nature of the catalysts was confirmed by X-ray absorption spectroscopy (XAS) and energy-dispersive X-ray spectroscopy (STEM-EDS) elemental mapping. The interplay between the chelate structure on the graphene surface and its metal binding ability has also been investigated by a combination of experimental and computational studies. The defined ligands on the graphene surfaces enable the formation of structurally precise heterogeneous molecular catalysts. The direct attachment of the isoxazoline functional group on the graphene surfaces provides strong electronic coupling between the chelated metal species and the conductive carbon nanomaterial support. We demonstrate that the metal-chelated carbon nanomaterials are effective heterogeneous catalysts in the oxygen evolution reaction with low overpotentials and tunable catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Persistent Friedel oscillations in graphene due to a weak magnetic field

Two opposite chiralities of Dirac electrons in a two-dimensional (2D) graphene sheet modify the Friedel oscillations strongly: electrostatic potential around an impurity in graphene decays much faster than in 2D electron gas. At distances $\textit{r}$ much larger than the de Broglie wavelength, it decays as 1/$r^3$. Here we show that a weak uniform magnetic field affects the Friedel oscillations in an anomalous way. It creates a field-dependent contribution which is dominant in a parametrically large spatial interval $p^{–1}_0 ≲ r ≲ k_Fl^2$, where $\textit{l}$ is the magnetic length, $k_F$ is Fermi momentum, and $p^{–1}_0 = (k_Fl)^{4/3} /k_F$. Moreover, in this interval, the field-dependent oscillations do not decay with distance. The effect originates from a spin-dependent magnetic phase accumulated by the electron propagator. Further, the obtained phase may give rise to novel interaction effects in transport and thermodynamic characteristics of graphene and graphene-based heterostructures.

36 MATERIALS SCIENCE↗

Imaging conductive nano-domains induced by Gd intercalation in epitaxial bilayer graphene

We report nano-infrared (IR) imaging and spectroscopy of epitaxial bilayer graphene (BLG) on silicon carbide (SiC) partially intercalated with gadolinium (Gd). Gd intercalation produces a high density of nanoscale conducting domains that exhibit pronounced IR enhancement at frequencies above the SiC phonon resonance and pronounced amplitude suppression at the resonance. Both effects originate from the increased local optical conductivity induced by Gd. Quantitative modeling of the nano-IR spectra shows that the conductivity of intercalated regions is enhanced by more than a factor of two relative to pristine BLG. This enhancement is attributed to the electronic decoupling of the graphene layers combined with substantial charge transfer from the intercalated atoms. These results demonstrate that controlled metal intercalation enables spatially resolved tuning of the electronic and optical responses of wafer-scale graphene, providing a versatile platform for graphene-based optoelectronic and nanophotonic applications.

Fralaide, Michael [Ames Laboratory, and Iowa State↗

Imaging supermoiré relaxation in helical trilayer graphene

In twisted van der Waals materials, local atomic relaxation can alter the underlying electronic structure. Characterizing lattice reconstruction and its susceptibility to strain is essential for understanding emergent electronic states, especially in multilayers in which interference between moiré lattices yields larger supermoiré patterns whose energy is highly sensitive to local stacking. Here, in this study, we image spatial modulations in the electronic character of helical trilayer graphene, which indicate relaxation into a superstructure of large domains with uniform moiré periodicity. We show that the supermoiré domain size is increased by strain and can be altered in the same device while preserving the local properties within each domain. Finally, we observe a higher conductance at the domain boundaries, consistent with predictions that they host counterpropagating edge modes. Our work provides a real-space visualization of moiré-periodic domains, reveals two independently tunable length scales and demonstrates strain engineering as a route towards designing correlated topological networks at the supermoiré scale.

36 MATERIALS SCIENCE↗

Controlled catalyst-transfer polymerization in graphene nanoribbon synthesis

Exercising direct control over the unusual electronic structures arising from quantum confinement effects in graphene nanoribbons (GNRs) is intimately linked to geometric boundary conditions imposed by the structure of the ribbon. Besides composition and position of substitutional dopant atoms, the symmetry of the unit cell, width, length, and termination of a GNR govern its electronic structure. Here, we present a rational design that integrates each of these interdependent variables within a modular bottom-up synthesis. Our hybrid chemical approach relies on a catalyst-transfer polymerization that establishes excellent control over length, width, and end groups. Complemented by a surface-assisted cyclodehydrogenation step, uniquely enabled by matrix-assisted direct (MAD) transfer protocols, geometry and functional handles encoded in a polymer template are faithfully mapped onto the structure of the corresponding GNR. Bond-resolved scanning tunneling microscopy (BRSTM) and spectroscopy (STS) validate the robust correlation between polymer template design and GNR electronic structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pore-Edge Tailoring of Single-Atom Iron–Nitrogen Sites on Graphene for Enhanced CO 2 Reduction

Hosting atomically dispersed nitrogen-coordinated iron sites (Fe-N 4 ) on graphene offers unique opportunities for driving electrochemical CO 2 reduction reaction (CO 2 RR) to CO. However, the strong adsorption of *CO on the Fe-N 4 site embedded in intact graphene limits current density due to slow CO desorption process. Herein, we report how the manipulation of pore edges on graphene alters the local electronic structure of isolated Fe-N 4 sites and improves their intrinsic reactivity for prompting CO generation. We demonstrate that constructing holes on graphene basal plane to support Fe-N 4 can significantly enhance its CO 2 RR compared to the pore-deficient graphene-supported counterpart, exhibiting a CO Faradaic efficiency of 94% and a turnover frequency of 1630 h -1 at 0.58 V vs RHE. Mechanistic studies reveal that the incorporation of pore edges results in the downshifting of the d-band center of Fe sites, which weakens the strength of the Fe-C bond when the *CO intermediate adsorbs on edge-hosted Fe-N 4 , thus boosting the CO desorption and evolution rates. These findings suggest that engineering local support structure renders a way to design high-performance single-atom catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bottom‐Up Synthesized Nanoporous Graphene Transistors

Abstract Nanoporous graphene (NPG) can exhibit a uniform electronic band gap and rationally‐engineered emergent electronic properties, promising for electronic devices such as field‐effect transistors (FETs), when synthesized with atomic precision. Bottom‐up, on‐surface synthetic approaches developed for graphene nanoribbons (GNRs) now provide the necessary atomic precision in NPG formation to access these desirable properties. However, the potential of bottom‐up synthesized NPG for electronic devices has remained largely unexplored to date. Here, FETs based on bottom‐up synthesized chevron‐type NPG (C‐NPG), consisting of ordered arrays of nanopores defined by laterally connected chevron GNRs, are demonstrated. C‐NPG FETs show excellent switching performance with on–off ratios exceeding 10 4 , which are tightly linked to the structural quality of C‐NPG. The devices operate as p‐type transistors in the air, while n‐type transport is observed when measured under vacuum, which is associated with reversible adsorption of gases or moisture. Theoretical analysis of charge transport in C‐NPG is also performed through electronic structure and transport calculations, which reveal strong conductance anisotropy effects in C‐NPG. The present study provides important insights into the design of high‐performance graphene‐based electronic devices where ballistic conductance and conduction anisotropy are achieved, which could be used in logic applications, and ultra‐sensitive sensors for chemical or biological detection.

Mutlu, Zafer↗

Transient Studies of Nonequilibrium Transport in Two-Dimensional Semiconductors

The overarching objective of research under DOE support has been to investigate emergent carrier phenomena in different two-dimensional (2D) systems, under conditions where they are driven far from equilibrium. The description of nonequilibrium transport has long represented one of the most enduring challenges in condensed-matter physics, in large part due to the need to invoke the role of complex many-body phenomena (electron-phonon and electron-electron coupling) in this regime. In this project, we have explored aspects of this problem in a variety of different two-dimensional systems. These include the modulation-doped two-dimensional electrons gas, or 2DEG, in GaAs/AlGaAs heterostructures; the electron and hole systems in graphene and its related hetero-structures, and; the strongly-confined electron layers in transition-metal dichalcogenide (MoS 2 and WS 2 ) and trichalcogenide (TiS 3 ) materials. Significant understanding has been achieved in a number of different areas, as we elaborate upon in subsequent sections of this proposal: Nanoscale spectroscopy of defect-related barriers in MoS2 Negative differential conductance due to inter-valley scattering in WS 2 under high fields Incipient localization due to scattering from frozen-phonon disorder in quantum point contacts High-field transient transport in graphene/hexagonal BN heterostructures Universal voltage scaling of quantum corrections in graphene under nonequilibrium A defining feature of much of this research has been an approach to problem solving in which novel experimental techniques (such as transient electrical pulsing and scanning-probe microscopy) are combined with the development (in collaboration with colleagues from condensed-matter theory) of sophisticated models, a strategy that we propose to continue in our future research. In recent years, we have developed an increasing capacity for handling atomically-thin materials, and their van der Waals systems, a capacity that is reflected in the balance of topics listed above.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Moiré nematic phase in twisted double bilayer graphene

Graphene moiré superlattices display electronic flat bands. At integer fillings of these flat bands, energy gaps due to strong electron-electron interactions are generally observed. However, the presence of other correlation-driven phases in twisted graphitic systems at non-integer fillings is unclear. Here, we report the existence of threefold rotational symmetry breaking in twisted double bilayer graphene. Using spectroscopic imaging over large and uniform areas to characterize the direction and degree of C 3 symmetry breaking, we find it to be prominent only at energies corresponding to the flat bands and nearly absent in the remote bands. We demonstrate that the magnitude of the rotational symmetry breaking does not depend on the degree of the heterostrain or the displacement field, being instead a manifestation of an interaction-driven electronic nematic phase. We show that the nematic phase is a primary order that arises from the normal metal state over a wide range of doping away from charge. Furthermore, our modelling suggests that the nematic instability is not associated with the local scale of the graphene lattice, but is an emergent phenomenon at the scale of the moiré lattice.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗