Graphene, a single atomic layer of graphitic carbon, has attracted intense attention due to its extraordinary properties that make it a suitable material for a wide range of technological applications. Large-area graphene films, which are necessary for industrial applications, are typically polycrystalline, that is, composed of single-crystalline grains of varying orientation joined by grain boundaries. Here, we present a review of the large body of research reported in the past few years on polycrystalline graphene. We discuss its growth and formation, the microscopic structure of grain boundaries and their relations to other types of topological defects such as dislocations. The review further covers electronic transport, optical and mechanical properties pertaining to the characterizations of grain boundaries, and applications of polycrystalline graphene. We also discuss research, still in its infancy, performed on other 2D materials such as transition metal dichalcogenides, and offer perspectives for future directions of research.
Most materials in available macroscopic quantities are polycrystalline. Graphene, a recently discovered two-dimensional form of carbon with strong potential for replacing silicon in future electronics, is no exception. There is growing evidence of the polycrystalline nature of graphene samples obtained using various techniques. Grain boundaries, intrinsic topological defects of polycrystalline materials, are expected to dramatically alter the electronic transport in graphene. Here, we develop a theory of charge carrier transmission through grain boundaries composed of a periodic array of dislo…
Lacking a band gap largely limits the application of graphene in electronic devices. Previous study shows that grain boundaries (GBs) in polycrystalline graphene can dramatically alter the electrical properties of graphene. Here, we investigate the band structure of polycrystalline graphene tuned by externally imposed strains and intrinsic mismatch strains at the GB by density functional theory (DFT) calculations. We found that graphene with symmetrical GBs typically has zero band gap even with large uniaxial and biaxial strain. However, some particular asymmetrical GBs can open a band gap in …
The low-temperature thermal conductivity in polycrystalline graphene is theoretically studied. The contributions from three branches of acoustic phonons are calculated by taking into account scattering on sample borders, point defects and grain boundaries. Phonon scattering due to sample borders and grain boundaries is shown to result in a $T^α$-behaviour in the thermal conductivity where $α$ varies between 1 and 2. This behaviour is found to be more pronounced for nanosized grain boundaries. PACS: 65.80.Ck, 81.05.ue, 73.43.Cd
We report graphene films composed mostly of one or two layers of graphene grown by controlled carbon precipitation on the surface of polycrystalline Ni thin films during atmospheric chemical vapor deposition(CVD). Controlling both the methane concentration during CVD and the substrate cooling rate during graphene growth can significantly improve the thickness uniformity. As a result, one- or two- layer graphene regions occupy up to 87% of the film area. Single layer coverage accounts for 5-11% of the overall film. These regions expand across multiple grain boundaries of the underlying polycrys…
First principles calculations, employed to address the properties of polycrystalline graphene, indicate that the electronic structure of tilt grain boundaries in this system displays a rather complex evolution towards graphene bulk, as the tilt angle decreases, with the generation of a new Dirac point at the Fermi level, and an anisotropic Dirac cone of low energy excitations. Moreover, the usual Dirac point at the {\bf K} point falls below the Fermi level, and rises towards it as the tilt angle decreases. Further, our calculations indicate that the grain-boundary formation energy behaves non-…
Graphene has drawn wide attention due to its exceptional thermal conductivity but complete understanding of thermal characteristics of polycrystalline graphene is still elusive to date. For the first time, herein, we have systematically studied the effect of temperature on the thermal conductance behavior of polycrystalline graphene for a range of grain sizes and grain boundary types, by using non-equilibrium molecular dynamics simulations. It is noted that increasing the tempera-ture remarkably enhances thermal boundary conductance (Kapitza conductance) across grain boundaries while it deteri…
Aharonov-Bohm (AB) interferences in the quantum Hall regime can be achieved, provided that electrons are able to transmit between two edge channels in nanostructures. Pioneering approaches include quantum point contacts in 2DEG systems, bipolar graphene p-n junctions, and magnetic field heterostructures. In this work, defect scattering is proposed as an alternative mechanism to achieve AB interferences in polycrystalline graphene. Indeed, due to such scattering, the extended defects across the sample can act as tunneling paths connecting quantum Hall edge channels. Consequently, strong AB osci…
Defects in solid commonly limit mechanical performance of the material. However, recent measurements reported that the extraordinarily high strength of graphene is almost retained with the presence of grain boundaries. We clarify in this work that lattice defects in the grain boundaries and distorted geometry thus induced define the mechanical properties characterized under specific loading conditions. Atomistic simulations and theoretical analysis show that tensile tests measure in-plane strength that is governed by defect-induced stress buildup, while nanoindentation probes local strength un…
In this Letter, both the manipulation of valley-polarized currents and the optical-like behaviors of Dirac fermions are theoretically explored in polycrystalline graphene. When strain is applied, the misorientation between two graphene domains separated by a grain boundary can result in a mismatch of their electronic structures. Such a discrepancy manifests itself in a strong breaking of the inversion symmetry, leading to perfect valley polarization in a wide range of transmission directions. In addition, these graphene domains act as different media for electron waves, offering the possibilit…
Grain boundaries in graphene are inherent in wafer-scale samples prepared by chemical vapor deposition. They can strongly influence the mechanical properties and electronic and heat transport in graphene. In this work, we employ extensive molecular dynamics simulations to study thermal transport in large suspended polycrystalline graphene samples. Samples of different controlled grain sizes are prepared by a recently developed efficient multiscale approach based on the phase field crystal model. In contrast to previous works, our results show that the scaling of the thermal conductivity with t…
Graphene grown by chemical vapor deposition (CVD) is the most promising material for industrial-scale applications based on graphene monolayers. It also holds promise for spintronics; despite being polycrystalline, spin transport in CVD graphene has been measured over lengths up to 30 $μ$m, which is on par with the best measurements made in single-crystal graphene. These results suggest that grain boundaries (GBs) in CVD graphene, while impeding charge transport, may have little effect on spin transport. However, to date very little is known about the true impact of disordered networks of GBs …
The observation of large nonlocal resistances near the Dirac point in graphene has been related to a variety of intrinsic Hall effects, where the spin or valley degrees of freedom are controlled by symmetry breaking mechanisms. Engineering strong spin or valley Hall signals on scalable graphene devices could stimulate further practical developments of spin- and valleytronics. Here we report on scale-invariant nonlocal transport in large-scale chemical vapour deposition graphene under an applied external magnetic field. Contrary to previously reported Zeeman spin Hall effect, our results are ex…
We extend the phase field crystal (PFC) framework to quantitative modeling of polycrystalline graphene. PFC modeling is a powerful multiscale method for finding the ground state configurations of large realistic samples that can be further used to study their mechanical, thermal or electronic properties. By fitting to quantum-mechanical density functional theory (DFT) calculations, we show that the PFC approach is able to predict realistic formation energies and defect structures of grain boundaries. We provide an in-depth comparison of the formation energies between PFC, DFT and molecular dyn…
We use numerical simulations to predict peculiar magnetotransport fingerprints in polycrystalline graphene, driven by the presence of grain boundaries of varying size and orientation. The formation of Landau levels is shown to be restricted by the polycrystalline morphology, requiring the magnetic length to be smaller than the average grain radius. The nature of localization is also found to be unusual, with strongly localized states at the center of Landau levels (including the usually highly robust zero-energy state) and extended electronic states lying between Landau levels. These extended …
We have revealed the decisive role of grain-boundary-induced strain fields in electron scattering in polycrystalline graphene. To this end, we have formulated the model based on Boltzmann transport theory which properly takes into account the microscopic structure of grain boundaries (GB) as a repeated sequence of heptagon-pentagon pairs. The effect of strain field is described within the deformation potential theory. For comparison, we consider the scattering due to electrostatic potential of charged grain boundary. We show that at naturally low GB charges the deformation potential scattering…
We report on the observation of strong backscattering of charge carriers in the quantum Hall regime of polycrystalline graphene grown by chemical vapor deposition, which alters the accuracy of the Hall resistance quantization. The temperature and magnetic field dependence of the longitudinal conductivity exhibits unexpectedly smooth power law behaviors, which are incompatible with a description in terms of variable range hopping or thermal activation, but rather suggest the existence of extended or poorly localized states at energies between Landau levels. Such states could be caused by the hi…
Grain boundaries are commonly observed in carbon nanostructures, but their influence on thermal and electric properties are still not completely understood. Using a combined approach of density functional tight-binding theory and non-equilibrium Green functions we investigate electron and phonon transport in carbon based systems. In this work, quantum transport and thermoelectric properties are summarized for graphene sheets, graphene nanoribbons and carbon nanotubes with a variety of grain boundary types in a wide temperature range. Motivated by previous findings that disorder scatters phonon…
A theoretical model supported by experimental results explains the dependence of the Raman scattering signal on the evolution of structural parameters along the amorphization trajectory of polycrystalline graphene systems. Four parameters rule the scattering efficiencies, two structural and two related to the scattering dynamics. With the crystallite sizes previously defined from X-ray diffraction and microscopy experiments, the three other parameters (the average grain boundaries width, the phonon coherence length, and the electron coherence length) are extracted from the Raman data with the …
The strong interest in graphene has motivated the scalable production of high quality graphene and graphene devices. Since large-scale graphene films synthesized to date are typically polycrystalline, it is important to characterize and control grain boundaries, generally believed to degrade graphene quality. Here we study single-crystal graphene grains synthesized by ambient CVD on polycrystalline Cu, and show how individual boundaries between coalescing grains affect graphene's electronic properties. The graphene grains show no definite epitaxial relationship with the Cu substrate, and can c…
We develop a device model for pixelless converters of far/mid-infrared radiation (FIR/MIR) images into near-infrared/visible (NIR/VIR) images. These converters use polycrystalline graphene layers (PGLs) immersed in the van der Waals (vdW) materials integrated with light emitting diode (LED). The PGL serves as an element of the PGL infrared photodetector (PGLIP) sensitive to the incoming FIR/MIR due to the interband absorption. The spatially non-uniform photocurrent generated in the PGLIP repeats (mimics) the non-uniform distribution (image) created by the incident FIR/MIR. The injection of the…
Grain boundaries (GBs) are ubiquitous in polycrystalline graphene materials obtained by various growth methods. It has been shown previously that considerable electrical transport gap can be opened by grain boundaries. On the other hand, polycrystalline graphene with GBs is an atomically thin membrane that can sustain extraordinary amount of strain. Here, by using atomistic quantum transport numerical simulations, we examine modulation of electrical transport properties of graphene GBs. The results indicate the modulation of transport gap and electrical conductance strongly depends on the topo…
Apart from its unique and exciting electronic properties, many sensor based applications of graphene are purely based on its mechanical and structural properties. Here we report a numerical and analytical study of a void in amorphous (small domain polycrystalline) graphene, and show that the energetics of a void is a balance between the line tension cost versus the increased area gain. Using the concepts of classical nucleation theory, we show that the critical radius of a void formed in amorphous graphene at constant pressure is simply the ratio of line tension at the void and the applied pre…
We systematically investigate the transmission of charge carriers across the grain-boundary defects in polycrystalline graphene by means of the Landauer-Büttiker formalism within the tight-binding approximation. Calculations reveal a strong suppression of transmission at low energies upon decreasing the density of dislocations with the smallest Burger's vector ${\mathbf b}=(1,0)$. The observed transport anomaly is explained from the point of view of back-scattering due to localized states of topological origin. These states are related to the gauge field associated with all dislocations charac…
We investigate the ability of frame-invariant amplitude equations [G. H. Gunaratne, Q. Ouyang, and H. Swinney, Phys. Rev. E {\bf 50}, 2802 (1994)] to describe quantitatively the evolution of polycrystalline microstructures and we extend this approach to include the interaction between composition and stress. Validations for elemental materials include studies of the Asaro-Tiller-Grinfeld morphological instability of a stressed crystal surface, polycrystalline growth from the melt, grain boundary energies over a wide range of misorientation, and grain boundary motion coupled to shear deformatio…
We demonstrate how self-assembled monolayers of aromatic molecules on copper substrates can be converted into high-quality single-layer graphene using low-energy electron irradiation and subsequent annealing. We characterize this two-dimensional solid state transformation on the atomic scale and study the physical and chemical properties of the formed graphene sheets by complementary microscopic and spectroscopic techniques and by electrical transport measurements. As substrates we successfully use Cu(111) single crystals and the technologically relevant polycrystalline copper foils.
We present a physics based multiscale materials-to-systems model for polycrystalline $PbSe$ photodetectors that connects fundamental material properties to circuit level performance metrics. From experimentally observed film structures and electrical characterization, we first develop a bandstructure model that explains carrier-type inversion and large carrier lifetimes in sensitized films. The unique bandstructure of the photosensitive film causes separation of generated carriers with holes migrating to the inverted $PbSe|PbI_2$ interface, while electrons are trapped in the bulk of the film i…
We investigate the influence of grain boundaries (GBs), line defects (LDs), and chirality on thermal transport in graphene using non-equilibrium Green's functions. At room temperature the ballistic thermal conductance is ~4.2 GW/m^2/K, and single GBs or LDs yield transmission from 50-80% of this value. LDs with carbon atom octagon defects have lower thermal transmission than GBs with pentagon and heptagon defects. We apply our findings to study the thermal conductivity of polycrystalline graphene for practical applications, and find that the type and size of GBs play an important role when gra…
Enhancing Unconventional Spin-Orbit Torque Efficiency: Numerical Study on the Influence of Crystallographic Texture and Polycrystalline Effects on Low-Symmetry Materials
We have investigated the lattice thermal transport across the asymmetric tilt grain boundary between armchair and zigzag graphene by nonequilibrium molecular dynamics (NEMD). We have observed significant temperature drop and ultra-low temperature-dependent thermal boundary resistance. More importantly, we find an unexpected thermal rectification phenomenon. The thermal conductivity and Kapitza conductance is direction-dependent. The effect of thermal rectification could be amplified by increasing the difference of temperature imposed on two sides. Our results propose a promising kind of therma…
In the framework of the suggested in [arxiv:1803.08247 [cond-mat.mtrl-sci]] statistical theory of the equilibrium flow stress, including yield strength, $σ_y$, of polycrystalline materials under quasi-static (in case of tensile strain) plastic deformation in dependence on average size, d, of the crystallites (grains) in the range, $10^{-8}$ m - $10^{-2}$ m. it is found the coincidences of the theoretical and experimental data of $σ_y$ for the materials with BCC ($α$- Fe), FCC (Cu, Al, Ni) and HCP ($α$-Ti, Zr) crystal lattice at T=300K. The temperature dependence of the strength characteristics…
We have used a multi-scale physics-based model to predict how the grain size and different grain boundary morphologies of polycrystalline graphene will impact the performance metrics of graphene field-effect transistors. We show that polycrystallinity has a negative impact on the transconductance, which translates to a severe degradation of the maximum and cutoff frequencies. On the other hand, polycrystallinity has a positive impact on current saturation, and a negligible effect on the intrinsic gain. These results reveal the complex role played by graphene grain boundaries, and can be used t…
Using full potential density functional theory calculations we have investigated the structural and electronic properties of graphene and some other graphene-like materials, viz., monolayer of SiC, GeC, BN, AlN, GaN, ZnO, ZnS and ZnSe. We hope, with the advancement of material synthesis techniques, some these new materials will be synthesized in the near future for potential applications in various nano-devices.
We report high room-temperature mobility in single layer graphene grown by Chemical Vapor Deposition (CVD) after wet transfer on SiO$_2$ and hexagonal boron nitride (hBN) encapsulation. By removing contaminations trapped at the interfaces between single-crystal graphene and hBN, we achieve mobilities up to$\sim70000cm^2 V^{-1} s^{-1}$ at room temperature and$\sim120000cm^2 V^{-1} s^{-1}$ at 9K. These are over twice those of previous wet transferred graphene and comparable to samples prepared by dry transfer. We also investigate the combined approach of thermal annealing and encapsulation in po…
Fe$_{3}$GeTe$_{2}$ is a two-dimensional van der Waals material with a ferromagnetic ground state and a maximum transition temperature $T_{\mathrm{c}}\sim225$ K. However, when Fe$_{3}$GeTe$_{2}$ is synthesized lower values of $T_{\mathrm{c}}$ are often reported. This is attributed to a deficiency in the Fe at the 2c site in the crystal structure. Here we investigate the effect of Fe deficiency and the substitution of Co for Fe on the magnetic properties of this system. We have synthesized both polycrystalline material and single crystals by chemical vapor transport and the flux method, with the…
Since the discovery of graphene -a single layer of carbon atoms arranged in a honeycomb lattice - it was clear that this truly is a unique material system with an unprecedented combination of physical properties. Graphene is the thinnest membrane present in nature -just one atom thick- it is the strongest material, it is transparent and it is a very good conductor with room temperature charge mobilities larger than the typical mobilities found in silicon. The significance played by this new material system is even more apparent when considering that graphene is the thinnest member of a larger …
Single defects in diamond and especially negatively charged nitrogen vacancy (NV) centers are very promising quantum systems with wide applications in physics and biology. It was shown that their coherence properties can be strongly improved by growing ultrapure diamond with low concentration of parasitic spins associated with nitrogen electron spins and nuclear spins related to $^{13}$C carbon isotope. Here we report a high quality $^{12}$C-enriched polycrystalline CVD diamond material with properties comparable with single crystals. We find single NVs in the grains of this material, which sh…
In spite of their importance for understanding phonon transport phenomena in thin films and polycrystalline solids, the effects of boundary roughness scattering on phonon specularity and coherence are poorly understood because there is no general method for predicting their dependence on phonon momentum, frequency, branch and boundary morphology. Using the recently formulated atomistic S-matrix method, we develop a theory of boundary roughness scattering to determine the mode-resolved phonon coherence and specularity parameters from the scattering amplitudes. To illustrate the theory, we apply…
Nano-carbon materials are investigated intensively. In this paper, the edge-state in nanographene materials with zigzag edges is studied theoretically. In particular, while the inter-layer interactions are considered, we prove that edge states exist at the energy of the Dirac point in the doubly stacked nanographene, and in the case of the infinitely-wide lower layer case. This property applies both for the A-B and A-C stackings.
The technical breakthrough in synthesizing graphene by chemical vapor deposition methods (CVD) has opened up enormous opportunities for large-scale device applications. In order to improve the electrical properties of CVD graphene grown on copper (Cu-CVD graphene), recent efforts have focussed on increasing the grain size of such polycrystalline graphene films to 100 micrometers and larger. While an increase in grain size and hence, a decrease of grain boundary density is expected to greatly enhance the device performance, here we show that the charge mobility and sheet resistance of Cu-CVD gr…
The success of graphene for nanopore DNA sequencing has shown that it is possible to explore other potential single- and few-atom thick layers of 2D materials beyond graphene, and also that these materials can exhibit fascinating and technologically useful properties for DNA base detection that are superior to those of graphene. In this article, we review the state-of-the art of DNA base detection using 2D materials beyond graphene. Initially, we present an overview of nanopore-based DNA sequencing methods using biological and solid-state nanopores, and discuss several challenges that limit th…
Graphene-metal nanoparticle hybrid materials potentially display not only the unique properties of metal nanoparticles and those of graphene, but also additional novel properties due to the interaction between graphene and nanoparticles. This study shows that gold nanoislands can be used to tailor the local electronic properties of graphene. Graphene on crystalline gold nanoislands exhibits moiré superlattices, which generate secondary Dirac points in the local density of states. Conversely, the graphene covered gold regions undergo a polycrystalline to Au(111) phase transition upon annealing.…
Chemical vapor deposition (CVD) has been proposed for large-scale graphene synthesis for practical applications. However, the inferior electronic properties of CVD graphene are one of the key problems to be solved. In this study, we present a detailed study on the electronic properties of high-quality single crystal monolayer graphene. The graphene is grown by CVD on copper using a cold-wall reactor and then transferred to Si/SiO2. Our low-temperature magneto-transport data demonstrate that the characteristics of the measured single-crystal CVD graphene samples are superior to those of polycry…
