Characterization of the Lipid Structure and Fluidity of Lipid Membranes on Epitaxial Graphene and Their Correlation to Graphene Features.

Graphene has been recognized as an enhanced platform for biosensors because of its high electron mobility. To integrate active membrane proteins into graphene-based materials for such applications, graphene's surface must be functionalized with lipids to mimic the biological environment of these proteins. Several studies have examined supported lipids on various types of graphene and obtained conflicting results for the lipid structure. Here, we present a correlative characterization technique based on fluorescence measurements in a Raman spectroscopy setup to study the lipid structure and dynamics on epitaxial graphene. Compared to other graphene variations, epitaxial graphene is grown on a substrate more conducive to production of electronics and offers unique topographic features. On the basis of experimental and computational results, we propose that a lipid sesquilayer (1.5 bilayer) forms on epitaxial graphene and demonstrate that the distinct surface features of epitaxial graphene affect the structure and diffusion of supported lipids.

Distinctive microfossil supports early Paleoproterozoic rise in complex cellular organisation.

The great oxidation event (GOE), ~2.4 billion years ago, caused fundamental changes to the chemistry of Earth's surface environments. However, the effect of these changes on the biosphere is unknown, due to a worldwide lack of well-preserved fossils from this time. Here, we investigate exceptionally preserved, large spherical aggregate (SA) microfossils permineralised in chert from the c. 2.4 Ga Turee Creek Group in Western Australia. Field and petrographic observations, Raman spectroscopic mapping, and in situ carbon isotopic analyses uncover insights into the morphology, habitat, reproduction and metabolism of this unusual form, whose distinctive, SA morphology has no known counterpart in the fossil record. Comparative analysis with microfossils from before the GOE reveals the large SA microfossils represent a step-up in cellular organisation. Morphological comparison to extant micro-organisms indicates the SAs have more in common with coenobial algae than coccoidal bacteria, emphasising the complexity of this microfossil form. The remarkable preservation here provides a unique window into the biosphere, revealing an increase in the complexity of life coinciding with the GOE.

Multi-wavelength Raman microscopy of nickel-based electron transport in cable bacteria.

Cable bacteria embed a network of conductive protein fibers in their cell envelope that efficiently guides electron transport over distances spanning up to several centimeters. This form of long-distance electron transport is unique in biology and is mediated by a metalloprotein with a sulfur-coordinated nickel (Ni) cofactor. However, the molecular structure of this cofactor remains presently unknown. Here, we applied multi-wavelength Raman microscopy to identify cell compounds linked to the unique cable bacterium physiology, combined with stable isotope labeling, and orientation-dependent and ultralow-frequency Raman microscopy to gain insight into the structure and organization of this novel Ni-cofactor. Raman spectra of native cable bacterium filaments reveal vibrational modes originating from cytochromes, polyphosphate granules, proteins, as well as the Ni-cofactor. After selective extraction of the conductive fiber network from the cell envelope, the Raman spectrum becomes simpler, and primarily retains vibrational modes associated with the Ni-cofactor. These Ni-cofactor modes exhibit intense Raman scattering as well as a strong orientation-dependent response. The signal intensity is particularly elevated when the polarization of incident laser light is parallel to the direction of the conductive fibers. This orientation dependence allows to selectively identify the modes that are associated with the Ni-cofactor. We identified 13 such modes, some of which display strong Raman signals across the entire range of applied wavelengths (405-1,064 nm). Assignment of vibrational modes, supported by stable isotope labeling, suggest that the structure of the Ni-cofactor shares a resemblance with that of nickel bis(1,2-dithiolene) complexes. Overall, our results indicate that cable bacteria have evolved a unique cofactor structure that does not resemble any of the known Ni-cofactors in biology.

Tribochemistry of Diamond-like Carbon: Interplay between Hydrogen Content in the Film and Oxidative Gas in the Environment.

The lubricity of hydrogenated diamond-like carbon (HDLC) films is highly sensitive to the hydrogen (H) content in the film and the oxidizing gas in the environment. The tribochemical knowledge of HDLC films with two different H-contents (mildly hydrogenated vs highly hydrogenated) was deduced from the analysis of the transfer layers formed on the counter-surface during friction tests in O2 and H2O using Raman spectroscopic imaging and X-ray photoelectron spectroscopy (XPS). The results showed that, regardless of H-content in the film, shear-induced graphitization and oxidation take place readily. By analyzing the O2 and H2O partial pressure dependence of friction of HDLC with a Langmuir-type reaction kinetics model, the oxidation probability of the HDLC surface exposed by friction as well as the removal probability of the oxidized species by friction were determined. The HDLC film with more H-content exhibited a lower oxidation probability than the film with less H-content. The atomistic origin of this H-content dependence was investigated using reactive molecular dynamics simulations, which showed that the fraction of undercoordinated carbon species decreased as the H-content in the film increased, corroborating the lower oxidation probability of the highly-hydrogenated film. The H-content in the HDLC film influenced the probabilities of oxidation and material removal, both of which vary with the environmental condition.

Identifying the Local Atomic Environment of the "Cu3+" State in Alkaline Electrochemical Systems.

CuO-based catalysts are active for the oxygen evolution reaction (OER), although the active form of copper for the OER is still unknown. We combine operando Raman experiments and density functional theory (DFT) electronic structure calculations to determine the form of Cu(O)xOHy present under OER conditions. Raman spectra show a distinct feature related to the active "Cu3+" species, which is only present under highly oxidizing conditions. DFT is used to produce theoretical Raman standards and match the unique Raman feature of copper under OER potentials. This method identifies a range of Cu3+-containing compounds which match the distinct Raman feature. We then integrate experimental electrochemistry to progressively eliminate possible structures and determine the stoichiometry of the active form as CuOOH, which likely takes the form of a surface-adsorbed hydroxide on a CuO surface. Bader charge analysis, site-projected wavefunctions, and density of states analysis show that electron density is removed from O 2p orbitals upon hydroxide adsorption, suggesting that the electronic structure exhibits d9L Cu2+ behavior rather than the local electronic structure of a formal Cu3+.

Strong electron-phonon coupling driven pseudogap modulation and density-wave fluctuations in a correlated polar metal.

There is tremendous interest in employing collective excitations of the lattice, spin, charge, and orbitals to tune strongly correlated electronic phenomena. We report such an effect in a ruthenate, Ca3Ru2O7, where two phonons with strong electron-phonon coupling modulate the electronic pseudogap as well as mediate charge and spin density wave fluctuations. Combining temperature-dependent Raman spectroscopy with density functional theory reveals two phonons, B2P and B2M, that are strongly coupled to electrons and whose scattering intensities respectively dominate in the pseudogap versus the metallic phases. The B2P squeezes the octahedra along the out of plane c-axis, while the B2M elongates it, thus modulating the Ru 4d orbital splitting and the bandwidth of the in-plane electron hopping; Thus, B2P opens the pseudogap, while B2M closes it. Moreover, the B2 phonons mediate incoherent charge and spin density wave fluctuations, as evidenced by changes in the background electronic Raman scattering that exhibit unique symmetry signatures. The polar order breaks inversion symmetry, enabling infrared activity of these phonons, paving the way for coherent light-driven control of electronic transport.

Shear Modes in a 2D Polar Metal.

Low-frequency shear and breathing modes are important Raman signatures of two-dimensional (2D) materials, providing information on the number of layers and insights into interlayer interactions. We elucidate the nature of low-frequency modes in a 2D polar metal-2D Ga covalently bonded to a SiC substrate, using a first-principles Green's function-based approach. The low-frequency Raman modes are dominated by surface resonance modes, consisting primarily of out-of-phase shear modes in Ga, coupled to SiC phonons. Breathing modes are strongly coupled to the substrate and do not give rise to peaks in the phonon spectra. The highest-frequency shear mode blue-shifts significantly with increasing thickness, reflecting both an increase in the number of Ga layers and an increase in the effective interlayer force constant. The surface resonance modes evolve into localized 2D Ga modes as the phonon momentum increases. The predicted low-frequency modes are consistent with Raman measurements on 2D polar Ga.

Interlayer magnetophononic coupling in MnBi2Te4.

The emergence of magnetism in quantum materials creates a platform to realize spin-based applications in spintronics, magnetic memory, and quantum information science. A key to unlocking new functionalities in these materials is the discovery of tunable coupling between spins and other microscopic degrees of freedom. We present evidence for interlayer magnetophononic coupling in the layered magnetic topological insulator MnBi2Te4. Employing magneto-Raman spectroscopy, we observe anomalies in phonon scattering intensities across magnetic field-driven phase transitions, despite the absence of discernible static structural changes. This behavior is a consequence of a magnetophononic wave-mixing process that allows for the excitation of zone-boundary phonons that are otherwise 'forbidden' by momentum conservation. Our microscopic model based on density functional theory calculations reveals that this phenomenon can be attributed to phonons modulating the interlayer exchange coupling. Moreover, signatures of magnetophononic coupling are also observed in the time domain through the ultrafast excitation and detection of coherent phonons across magnetic transitions. In light of the intimate connection between magnetism and topology in MnBi2Te4, the magnetophononic coupling represents an important step towards coherent on-demand manipulation of magnetic topological phases.

Tunable 2D Group-III Metal Alloys.

Chemically stable quantum-confined 2D metals are of interest in next-generation nanoscale quantum devices. Bottom-up design and synthesis of such metals could enable the creation of materials with tailored, on-demand, electronic and optical properties for applications that utilize tunable plasmonic coupling, optical nonlinearity, epsilon-near-zero behavior, or wavelength-specific light trapping. In this work, it is demonstrated that the electronic, superconducting, and optical properties of air-stable 2D metals can be controllably tuned by the formation of alloys. Environmentally robust large-area 2D-Inx Ga1- x alloys are synthesized byConfinement Heteroepitaxy (CHet). Near-complete solid solubility is achieved with no evidence of phase segregation, and the composition is tunable over the full range of x by changing the relative elemental composition of the precursor. The optical and electronic properties directly correlate with alloy composition, wherein the dielectric function, band structure, superconductivity, and charge transfer from the metal to graphene are all controlled by the indium/gallium ratio in the 2D metal layer.

Correlating Raman spectral signatures with carrier mobility in epitaxial graphene: a guide to achieving high mobility on the wafer scale.

We report a direct correlation between carrier mobility and Raman topography of epitaxial graphene (EG) grown on silicon carbide (SiC). We show the Hall mobility of material on SiC(0001) is highly dependent on thickness and monolayer strain uniformity. Additionally, we achieve high mobility epitaxial graphene (18100 cm(2)/(V s) at room temperature) on SiC(0001) and show that carrier mobility depends strongly on the graphene layer stacking.

Oxide-Free Three-Dimensional Germanium/Silicon Core-Shell Metalattice Made by High-Pressure Confined Chemical Vapor Deposition.

Metalattices are crystalline arrays of uniform particles in which the period of the crystal is close to some characteristic physical length scale of the material. Here, we explore the synthesis and properties of a germanium metalattice in which the ∼70 nm periodicity of a silica colloidal crystal template is close to the ∼24 nm Bohr exciton radius of the nanocrystalline Ge replica. The problem of Ge surface oxidation can be significant when exploring quantum confinement effects or designing electronically coupled nanostructures because of the high surface area to volume ratio at the nanoscale. To eliminate surface oxidation, we developed a core-shell synthesis in which the Ge metalattice is protected by an oxide-free Si interfacial layer, and we explore its properties by transmission electron microscopy (TEM), Raman spectroscopy, and electron energy loss spectroscopy (EELS). The interstices of a colloidal crystal film grown from 69 nm diameter spherical silica particles were filled with polycrystalline Ge by high-pressure confined chemical vapor deposition (HPcCVD) from GeH4. After the SiO2 template was etched away with aqueous HF, the Ge replica was uniformly coated with an amorphous Si shell by HPcCVD as confirmed by TEM-EDS (energy-dispersive X-ray spectroscopy) and Raman spectroscopy. Formation of the shell prevents oxidation of the Ge core within the detection limit of XPS. The electronic properties of the core-shell structure were studied by accessing the Ge 3d edge onset using STEM-EELS. A blue shift in the edge onset with decreasing size of Ge sites in the metalattices suggests quantum confinement of the Ge core. The degree of quantum confinement of the Ge core depends on the void sizes in the template, which is tunable by using silica particles of varying size. The edge onset also shows a shift to higher energy near the shell in comparison with the Ge core. This shift along with the observation of Ge-Si vibrational modes in the Raman spectrum indicate interdiffusion of Ge and Si. Both the size of the voids in the template and core-shell interdiffusion of Si and Ge can in principle be tuned to modify the electronic properties of the Ge metalattice.

Low frequency Raman Spectroscopy for micron-scale and in vivo characterization of elemental sulfur in microbial samples.

Elemental sulfur (S(0)) is an important intermediate of the sulfur cycle and is generated by chemical and biological sulfide oxidation. Raman spectromicroscopy can be applied to environmental samples for the detection of S(0), as a practical non-destructive micron-scale method for use on wet material and living cells. Technical advances in filter materials enable the acquisition of ultra-low frequency (ULF) Raman measurements in the 10-100 cm-1 range using a single-stage spectrometer. Here we demonstrate the potency of ULF Raman spectromicroscopy to harness the external vibrational modes of previously unrecognized S(0) structures present in environmental samples. We investigate the chemical and structural nature of intracellular S(0) granules stored within environmental mats of sulfur-oxidizing γ-Proteobacteria (Thiothrix). In vivo intracellular ULF scans indicate the presence of amorphous cyclooctasulfur (S8), clarifying enduring uncertainties regarding the content of microbial sulfur storage globules. Raman scattering of extracellular sulfur clusters in Thiothrix mats furthermore reveals an unexpected abundance of metastable ß-S8 and γ-S8, in addition to the stable α-S8 allotrope. We propose ULF Raman spectroscopy as a powerful method for the micron-scale determination of S(0) structure in natural and laboratory systems, with a promising potential to shine new light on environmental microbial and chemical sulfur cycling mechanisms.

Integration of hexagonal boron nitride with quasi-freestanding epitaxial graphene: toward wafer-scale, high-performance devices.

Hexagonal boron nitride (h-BN) is a promising dielectric material for graphene-based electronic devices. Here we investigate the potential of h-BN gate dielectrics, grown by chemical vapor deposition (CVD), for integration with quasi-freestanding epitaxial graphene (QFEG). We discuss the large scale growth of h-BN on copper foil via a catalytic thermal CVD process and the subsequent transfer of h-BN to a 75 mm QFEG wafer. X-ray photoelectron spectroscopy (XPS) measurements confirm the absence of h-BN/graphitic domains and indicate that the film is chemically stable throughout the transfer process, while Raman spectroscopy indicates a 42% relaxation of compressive stress following removal of the copper substrate and subsequent transfer of h-BN to QFEG. Despite stress-induced wrinkling observed in the films, Hall effect measurements show little degradation (<10%) in carrier mobility for h-BN coated QFEG. Temperature dependent Hall measurements indicate little contribution from remote surface optical phonon scattering and suggest that, compared to HfO(2) based dielectrics, h-BN can be an excellent material for preserving electrical transport properties. Graphene transistors utilizing h-BN gates exhibit peak intrinsic cutoff frequencies >30 GHz (2.4× that of HfO(2)-based devices).

Nucleation of epitaxial graphene on SiC(0001).

A promising route for the synthesis of large-area graphene, suitable for standard device fabrication techniques, is the sublimation of silicon from silicon carbide at elevated temperatures (>1200 degrees C). Previous reports suggest that graphene nucleates along the (110n) plane, known as terrace step edges, on the silicon carbide surface. However, to date, a fundamental understanding of the nucleation of graphene on silicon carbide is lacking. We provide the first direct evidence that nucleation of epitaxial graphene on silicon carbide occurs along the (110n) plane and show that the nucleated graphene quality improves as the synthesis temperature is increased. Additionally, we find that graphene on the (110n) plane can be significantly thicker than its (0001) counterpart and appears not to have a thickness limit. Finally, we find that graphene along the (110n) plane can contain a high density of structural defects, often the result of the underlying substrate, which will undoubtedly degrade the electronic properties of the material. Addressing the presence of non-uniform graphene that may contain structural defects at terrace step edges will be key to the development of a large-scale graphene technology derived from silicon carbide.