Raman spectroscopy is an integral part of graphene research. It is used to determine the number and orientation of layers, the quality and types of edge, and the effects of perturbations, such as ...electric and magnetic fields, strain, doping, disorder and functional groups. This, in turn, provides insight into all sp(2)-bonded carbon allotropes, because graphene is their fundamental building block. Here we review the state of the art, future directions and open questions in Raman spectroscopy of graphene. We describe essential physical processes whose importance has only recently been recognized, such as the various types of resonance at play, and the role of quantum interference. We update all basic concepts and notations, and propose a terminology that is able to describe any result in literature. We finally highlight the potential of Raman spectroscopy for layered materials other than graphene.
The twisted index and topological saddles Bullimore, Mathew; Ferrari, Andrea E. V.; Kim, Heeyeon ...
The journal of high energy physics,
05/2022, Letnik:
2022, Številka:
5
Journal Article
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A
bstract
The twisted index of 3d
N
= 2 gauge theories on
S
1
×
Σ has an algebro-geometric interpretation as the Witten index of an effective supersymmetric quantum mechanics. In this paper, we ...consider the contributions to the supersymmetric quantum mechanics from topological saddle points in supersymmetric localisation of abelian gauge theories. Topological saddles are configurations where the matter fields vanish and the gauge symmetry is unbroken, which exist for non-vanishing effective Chern-Simons levels. We compute the contributions to the twisted index from both topological and vortex-like saddles points and show that their combination recovers the Jeffrey-Kirwan residue prescription for the twisted index and its wall-crossing.
We present a combined analytical and numerical study of the early stages (sub-100-fs) of the nonequilibrium dynamics of photoexcited electrons in graphene. We employ the semiclassical Boltzmann ...equation with a collision integral that includes contributions from electron-electron (e-e) and electron-optical phonon interactions. Taking advantage of circular symmetry and employing the massless Dirac fermion (MDF) Hamiltonian, we are able to perform an essentially analytical study of the e-e contribution to the collision integral. This allows us to take particular care of subtle collinear scattering processes-processes in which incoming and outgoing momenta of the scattering particles lie on the same line-including carrier multiplication (CM) and Auger recombination (AR). These processes have a vanishing phase space for two-dimensional MDF bare bands. However, we argue that electron-lifetime effects, seen in experiments based on angle-resolved photoemission spectroscopy, provide a natural pathway to regularize this pathology, yielding a finite contribution due to CM and AR to the Coulomb collision integral. Finally, we discuss in detail the role of physics beyond the Fermi golden rule by including screening in the matrix element of the Coulomb interaction at the level of the random phase approximation (RPA), focusing in particular on the consequences of various approximations including static RPA screening, which maximizes the impact of CM and AR processes, and dynamical RPA screening, which completely suppresses them.
Background
The integration of graphene in photovoltaic modules, fuel cells, batteries, supercapacitors, and devices for hydrogen generation offers opportunities to tackle challenges driven by the ...increasing global energy demand. Graphene’s two-dimensional (2D) nature leads to a theoretical surface-to-mass ratio of ~2600 m
2
/g, which combined with its high electrical conductivity and flexibility, gives it the potential to store electric charge, ions, or hydrogen. Other 2D crystals, such as transition metal chalcogenides (TMDs) and transition metal oxides, are also promising and are now gaining increasing attention for energy applications. The advantage of using such 2D crystals is linked to the possibility of creating and designing layered artificial structures with “on-demand” properties by means of spin-on processes, or layer-by-layer assembly. This approach exploits the availability of materials with metallic, semiconducting, and insulating properties.
Advances
The success of graphene and related materials (GRMs) for energy applications crucially depends on the development and optimization of production methods. High-volume liquid-phase exfoliation is being developed for a wide variety of layered materials. This technique is being optimized to control the flake size and to increase the edge-to-surface ratio, which is crucial for optimizing electrode performance in fuel cells and batteries. Micro- or nanocrystal or flake edge control can also be achieved through chemical synthesis. This is an ideal route for functionalization, in order to improve storage capacity. Large-area growth via chemical vapor deposition (CVD) has been demonstrated, producing material with high structural and electronic quality for the preparation of transparent conducting electrodes for displays and touch-screens, and is being evaluated for photovoltaic applications. CVD growth of other multicomponent layered materials is less mature and needs further development. Although many transfer techniques have been developed successfully, further improvement of high-volume manufacturing and transfer processes for multilayered heterostructures is needed. In this context, layer-by-layer assembly may enable the realization of devices with on-demand properties for targeted applications, such as photovoltaic devices in which photon absorption in TMDs is combined with charge transport in graphene.
Outlook
Substantial progress has been made on the preparation of GRMs at the laboratory level. However, cost-effective production of GRMs on an industrial scale is needed to create the future energy value chain. Applications that could benefit the most from GRMs include flexible electronics, batteries with efficient anodes and cathodes, supercapacitors with high energy density, and solar cells. The realization of GRMs with specific transport and insulating properties on demand is an important goal. Additional energy applications of GRMs comprise water splitting and hydrogen production. As an example, the edges of MoS
2
single layers can oxidize fuels—such as hydrogen, methanol, and ethanol—in fuel cells, and GRM membranes can be used in fuel cells to improve proton exchange. Functionalized graphene can be exploited for water splitting and hydrogen production. Flexible and wearable devices and membranes incorporating GRMs can also generate electricity from motion, as well as from water and gas flows.
Tailored GRMs for energy applications.
The ability to produce GRMs with desired specific properties paves the way to their integration in a variety of energy devices. Solution processing and chemical vapor deposition are the ideal means to produce thin films that can be used as electrodes in energy devices (such as
solar panels, batteries, fuel cells, or in hydrogen storage). Chemical synthesis is an attractive route to produce “active” elements in solar cell or thermoelectric devices.
Graphene and related two-dimensional crystals and hybrid systems showcase several key properties that can address emerging energy needs, in particular for the ever growing market of portable and wearable energy conversion and storage devices. Graphene’s flexibility, large surface area, and chemical stability, combined with its excellent electrical and thermal conductivity, make it promising as a catalyst in fuel and dye-sensitized solar cells. Chemically functionalized graphene can also improve storage and diffusion of ionic species and electric charge in batteries and supercapacitors. Two-dimensional crystals provide optoelectronic and photocatalytic properties complementing those of graphene, enabling the realization of ultrathin-film photovoltaic devices or systems for hydrogen production. Here, we review the use of graphene and related materials for energy conversion and storage, outlining the roadmap for future applications.
Layered materials power the cause
Methods for storing and converting energy, including fuel cells, solar cells, and water splitting, often benefit from having materials with a large surface area. When combined with a high surface reactivity, high conductivity, or useful optical properties, two-dimensional layered materials become of notable interest for a range of applications. Bonaccorso
et al.
review the progress that has been made using graphene and other layered or two-dimensional materials at laboratory scales and the challenges in producing these materials in industrially relevant quantities.
Science
, this issue
10.1126/science.1246501
We investigate the evolution of the Raman spectrum of defected graphene as a function of doping. Polymer electrolyte gating allows us to move the Fermi level up to 0.7 eV, as directly monitored by in ...situ Hall-effect measurements. For a given number of defects, we find that the intensities of the D and D′ peaks decrease with increasing doping. We assign this to an increased total scattering rate of the photoexcited electrons and holes, due to the doping-dependent strength of electron–electron scattering. We present a general relation between D peak intensity and defects valid for any doping level.
Graphene is at the center of an ever growing research effort due to its unique properties, interesting for both fundamental science and applications. A key requirement for applications is the ...development of industrial-scale, reliable, inexpensive production processes. Here we review the state of the art of graphene preparation, production, placement and handling. Graphene is just the first of a new class of two dimensional materials, derived from layered bulk crystals. Most of the approaches used for graphene can be extended to these crystals, accelerating their journey towards applications.
Quantum light emitters have been observed in atomically thin layers of transition metal dichalcogenides. However, they are found at random locations within the host material and usually in low ...densities, hindering experiments aiming to investigate this new class of emitters. Here, we create deterministic arrays of hundreds of quantum emitters in tungsten diselenide and tungsten disulphide monolayers, emitting across a range of wavelengths in the visible spectrum (610-680 nm and 740-820 nm), with a greater spectral stability than their randomly occurring counterparts. This is achieved by depositing monolayers onto silica substrates nanopatterned with arrays of 150-nm-diameter pillars ranging from 60 to 190 nm in height. The nanopillars create localized deformations in the material resulting in the quantum confinement of excitons. Our method may enable the placement of emitters in photonic structures such as optical waveguides in a scalable way, where precise and accurate positioning is paramount.
► Direct numerical simulations of multiphase flow at pore-scale are performed with the Volume Of Fluid (VOF) method. ► The VOF is able to model the transition from stable flow to viscous fingering. ► ...Common definitions of Darcy’s scale capillary pressure are inaccurate in presence of viscous effects and trapping. ► A definition based on the variation of the total interfacial energy provides a more accurate estimate of the macroscopic capillary pressure.
The flow of two immiscible fluids through a porous medium depends on the complex interplay between gravity, capillarity, and viscous forces. The interaction between these forces and the geometry of the medium gives rise to a variety of complex flow regimes that are difficult to describe using continuum models. Although a number of pore-scale models have been employed, a careful investigation of the macroscopic effects of pore-scale processes requires methods based on conservation principles in order to reduce the number of modeling assumptions. In this work we perform direct numerical simulations of drainage by solving Navier–Stokes equations in the pore space and employing the Volume Of Fluid (VOF) method to track the evolution of the fluid–fluid interface. After demonstrating that the method is able to deal with large viscosity contrasts and model the transition from stable flow to viscous fingering, we focus on the macroscopic capillary pressure and we compare different definitions of this quantity under quasi-static and dynamic conditions. We show that the difference between the intrinsic phase-average pressures, which is commonly used as definition of Darcy-scale capillary pressure, is subject to several limitations and it is not accurate in presence of viscous effects or trapping. In contrast, a definition based on the variation of the total surface energy provides an accurate estimate of the macroscopic capillary pressure. This definition, which links the capillary pressure to its physical origin, allows a better separation of viscous effects and does not depend on the presence of trapped fluid clusters.
We review recent work on Raman spectroscopy of graphite and graphene. We focus on the origin of the
D
and
G
peaks and the second order of the
D
peak. The
G
and
2
D
Raman peaks change in shape, ...position and relative intensity with number of graphene layers. This reflects the evolution of the electronic structure and electron–phonon interactions. We then consider the effects of doping on the Raman spectra of graphene. The Fermi energy is tuned by applying a gate-voltage. We show that this induces a stiffening of the Raman
G
peak for both holes and electrons doping. Thus Raman spectroscopy can be efficiently used to monitor number of layers, quality of layers, doping level and confinement.
Transition metal dichalcogenides (TMDs) are emerging as promising two-dimensional (2D) semiconductors for optoelectronic and flexible devices. However, a microscopic explanation of their ...photophysics, of pivotal importance for the understanding and optimization of device operation, is still lacking. Here, we use femtosecond transient absorption spectroscopy, with pump pulse tunability and broadband probing, to monitor the relaxation dynamics of single-layer MoS2 over the entire visible range, upon photoexcitation of different excitonic transitions. We find that, irrespective of excitation photon energy, the transient absorption spectrum shows the simultaneous bleaching of all excitonic transitions and corresponding red-shifted photoinduced absorption bands. First-principle modeling of the ultrafast optical response reveals that a transient bandgap renormalization, caused by the presence of photoexcited carriers, is primarily responsible for the observed features. Our results demonstrate the strong impact of many-body effects in the transient optical response of TMDs even in the low-excitation-density regime.
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