Enhanced Raman scattering of graphene on Ag nanoislands

The effect of Ag nanoislands on the Raman of graphene was investigated in this work. Compared with that on the bare silicon wafer, Raman enhancement was observed in the graphene film that covered on Ag/Si surface with nanoscale Ag islands, which would be induced by the localized plasmon resonance in Ag nanostructures. The interaction between the graphene sheet and Ag/Si substrate was further studied. The peak shift and line shape of Raman spectroscopy indicated a nonuniform strain distribution in the Ag/Si supported graphene film.     

Bioinspired few‐layer graphene prepared by chemical vapor deposition on femtosecond laser‐structured Cu foil

Inspired from butterfly wings that exhibit unique dewetting properties and brilliant structural color synchronously, we reported here the preparation of biomimetic few‐layer graphene films through a template‐directed chemical vapor deposition method using laser‐structured Cu foil as substrates. Hierarchical micronanostructures, including microscale stripes derived from the laser scanning and nanoscale laser‐induced periodic surface structures (LIPSS), formed on Cu foil after a simple femtosecond laser treatment. By tuning the laser power, the surface roughness of the resultant Cu foils can be well controlled. Using the laser structures Cu foil as templates, biomimetic few‐layer graphene films with both iridescence and superhydrophobicity have been successfully prepared. The present work may open up a new way to design and prepare structured graphene film in a biomimetic manner, and we deem that the bioinspired few‐layer graphene films may find broad applications in the near future.

     

Field emissions of graphene films deposited on different substrates by CVD system

<正>Graphene films are deposited on copper(Cu) and aluminum(Al) substrates,respectively,by using a microwave plasma chemical vapour deposition technique.Furthermore,these graphene films are characterized by a field emission type scanning electron microscope(FE-SEM),Raman spectra,and field emission(FE) I-V measurements.It is found that the surface morphologies of the films deposited on Cu and Al substrates are different:the field emission property of graphene film deposited on the Cu substrate is better than that on the Al substrate,and the lowest turn-on field of 2.4 V/μm is obtained for graphene film deposited on the Cu substrate.The macroscopic areas of the graphene samples are all above 400 mm~2.     

Raman spectroscopy study of twisted tetralayer graphene

We present a systematic Raman study of twisted tetralayer graphene (t(2 + 2)LG), under excitation of two laser lines. In t(2 + 2)LG samples, top Bernal stacked bilayer graphene (2LG stands for Bernal‐stacked bilayer graphene) twists different angle relative to bottom 2LG. It is found that 2D and 2D′ peaks of t(2 + 2)LG show positive wavenumber shift relative to those of 2LG. We propose a simplified electronic band structure for t(2 + 2)LG; interlayer interaction‐induced changing in electronic band structure can be used to understand the aforementioned spectral features. The electronic structures of t(2 + 2)LG samples are then probed from resonant Raman studies of 2D and 2D′ peaks using two laser lines; electronic dispersions in t(2 + 2)LG samples are given. Our study facilitates understanding of twist angle‐dependent electronic properties of tetralayer graphene superlattice. Copyright © 2016 John Wiley & Sons, Ltd.     

Transport properties in monolayer–bilayer–monolayer graphene planar junctions

The transport study of graphene based junctions has become one of the focuses in graphene research. There are two stacking configurations for monolayer–bilayer–monolayer graphene planar junctions. One is the two monolayer graphene contacting the same side of the bilayer graphene, and the other is the two-monolayer graphene contacting the different layers of the bilayer graphene. In this paper, according to the Landauer–Büttiker formula, we study the transport properties of these two configurations. The influences of the local gate potential in each part, the bias potential in bilayer graphene,the disorder and external magnetic field on conductance are obtained. We find the conductances of the two configurations can be manipulated by all of these effects. Especially, one can distinguish the two stacking configurations by introducing the bias potential into the bilayer graphene. The strong disorder and the external magnetic field will make the two stacking configurations indistinguishable in the transport experiment.     

Comparative study of single and multi domain CVD graphene using large‐area Raman mapping and electrical transport characterization

We systematically investigate the impact of granularity in CVD graphene films by performing Raman mapping and electrical characterization of single (SD) and multi domain (MD) graphene. In order to elucidate the quality of the graphene film, we study its regional variations using large‐area Raman mapping and compare the G and 2D peak positions of as‐transferred chemical vapor deposited (CVD) graphene on SiO₂ substrate. We find a similar upshift in wavenumber in both SD and MD graphene in comparison to freshly exfoliated graphene. In our case, doping could play the dominant role behind the observation of such upshifts rather than the influence due to strain. Interestingly, the impact of the polymer‐assisted wet transfer process is the same in both the CVD graphene types. The electrical characterization shows that SD graphene exhibits a substantially higher (a factor 5) field‐effect mobility when compared to MD graphene. We attribute the low sheet resistance and mobility enhancement to a decrease in charge carrier scattering thanks to a reduction of the number of grain boundaries and defects in SD graphene.     

Graphene films grown on sapphire substrates via solid source molecular beam epitaxy

A method for growing graphene on a sapphire substrate by depositing an SiC buffer layer and then annealing at high temperature in solid source molecular beam epitaxy (SSMBE) equipment was presented. The structural and electronic properties of the samples were characterized by reflection high energy diffraction (RHEED), X-ray diffraction Φ scans, Raman spectroscopy, and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. The results of the RHEED and Φ scan, as well as the Raman spectra, showed that an epitaxial hexagonal α-SiC layer was grown on the sapphire substrate. The results of the Raman and NEXAFS spectra revealed that the graphene films with the AB Bernal stacking structure were formed on the sapphire substrate after annealing. The layer number of the graphene was between four and five, and the thickness of the unreacted SiC layer was about 1--1.5 nm.     

Raman imaging on high‐quality graphene grown by hot‐filament chemical vapor deposition

We report the synthesis of high‐quality graphene on Cu foils using hot‐filament chemical vapor deposition technique and demonstrate that by suitably varying the CH₄ and H₂ flow rates, one can also obtain hydrogenated graphene. Micro‐Raman spectroscopy studies confirm the growth of monolayer graphene as inferred from the intensity ratio of 2D to G peak which is nearly four in unhydrogenated samples. Detailed Raman area mapping confirms the uniform coverage of monolayer graphene. The grown layer is also transferred onto a Si substrate over ~10 × 10 mm sq. area. The present results provide a leap in synthesis technology of high‐quality graphene and pave way for scaling up the process. Copyright © 2012 John Wiley & Sons, Ltd.     

Atmospheric pressure plasma treatment on graphene grown by chemical vapor deposition

We demonstrate the surface treatment of graphene using an atmospheric pressure plasma jet (APPJ) system. The graphene was synthesized by a thermal chemical vapor deposition with methane gas. A Mo foil and a SiO₂ wafer covered by Ni films were employed to synthesize monolayer and mixed-layered graphene, respectively. The home-built APPJ system was ignited using nitrogen gas to functionalize the graphene surface, and we studied the effect of different treatment times and interdistance between the plasma jet and the graphene surface. After the APPJ treatment, the hydrophobic character of graphene surface changed to hydrophilic. We found that the change is due to the formation of functionalities such as hydroxyl and carboxyl groups. Furthermore, it is worth noting that the nitrogen plasma treatment induced charge doping on graphene, and the pyridinic nitrogen component in the X-ray photoelectron spectroscopy spectrum was significantly enhanced. We conclude that the atmospheric pressure plasma treatment enables controlling the graphene properties without introducing surface defects.     

Raman spectroscopic studies of pulsed laser‐induced defect evolution in graphene

Raman spectra were obtained for graphene after irradiating the samples by pulsed laser (λ = 248 nm). Changes in the spectra were observed as the pulse laser energy density (PLED) was varied from 0.1 to 0.25 J/cm². Changes in bilayer graphene were accompanied by the appearance of the D peak and the broadening of the G peak. Changes in multilayer graphene are more profound as the Raman spectra changes from a multilayer to bilayer and subsequently to monolayer graphene in response to a slow increase in the PLED. The threshold PLED was found to be dependent on the number of graphene layers. We also irradiate graphene with very high PLED (much above the threshold), and the Raman spectra were found to be significantly changed. The G‐band became broader, and red shifted, while the intensity of the 2D‐band was drastically reduced and an intense defect‐related D peak appeared at about 1350 cm⁻¹. The laser ablation of graphene, both with low‐ and high‐energy intensity, is consistent with the reported theoretical predictions. Copyright © 2013 John Wiley & Sons, Ltd.     

Interlayer vacancy effects on the phonon modes in AB stacked bilayer graphene nanoribbon

We explore the effects of interlayer vacancy defects on the vibrational properties of Bernal (AB) stacking bilayer armchair graphene nanoribbons (BiAGNRs) using the forced vibrational method. It is observed that the Raman active longitudinal optical (LO) phonon of BiAGNR is shifted downward with the decrease of the ribbon width and an increase of the vacancy concentrations. We find that vacancies induce some new peaks in the low frequency regime of the phonon density of states. Our calculated typical mode patterns elucidate that the localized transverse optical phonon at the K-point is shifted towards the defect sites from the edges with increased vacancy concentrations. In addition, the impact of defect induced phonon modes on the specific heat capacity and thermal conductivity of BiAGNRs are discussed. These results present a new way of understanding the heat dissipation phenomena of graphene-based high-performance nanodevices and to clarify the Raman and the experiments related to the phonon properties.     

Influence of copper crystal surface on the CVD growth of large area monolayer graphene

We study the influence of the surface structure of copper single crystals on the growth of large area monolayer graphene by chemical vapor deposition (CVD) in ultra-high vacuum (UHV). Using atomic-resolution scanning tunneling microscopy (STM), we find that graphene grows primarily in registry with the underlying copper lattice for both Cu(111) and Cu(100). The graphene has a hexagonal superstructure on Cu(111) with a significant electronic component,whereas it has a linear superstructure on Cu(100). Graphene on Cu(111) forms a microscopically uniform sheet, the quality of which is determined by the presence of grain boundaries where graphene grains with different orientations meet. Graphene grown on Cu(100) under similar conditions does not form a uniform sheet and instead displays exposed nanoscale edges. Our results indicate the importance of the copper crystal structure on the microstructure of graphene films produced by CVD.     

Band topology and the quantum spin Hall effect in bilayer graphene

We consider bilayer graphene in the presence of spin-orbit coupling, in order to assess its behavior as a topological insulator. The first Chern number n for the energy bands of single-layer graphene and that for the energy bands of bilayer graphene are computed and compared. It is shown that for a given valley and spin, n for a Bernal-stacked bilayer is doubled with respect to that for the monolayer. This implies that this form of bilayer graphene will have twice as many edge states as single-layer graphene, which we confirm with numerical calculations and analytically in the case of an armchair terminated surface. Bernal-stacked bilayer graphene is a weak topological insulator, whose surface spectrum is susceptible to gap opening under spin-mixing perturbations. We assess the stability of the associated topological bulk state of bilayer graphene under various perturbations. In contrast, we show that AA-stacked bilayer graphene is not a topological insulator unless the spin-orbit coupling is bigger than the interlayer hopping. Finally, we consider an intermediate situation in which only one of the two layers has spin-orbit coupling, and find that although individual valleys have non-trivial Chern numbers for the case of Bernal stacking, the spectrum as a whole is not gapped, so the system is not a topological insulator.     

旋转双层石墨烯的电子结构

本文将第一性原理和紧束缚方法结合起来, 研究了层间不同旋转角度对双层石墨烯的电子能带结构和态密度的影响. 分析发现, 旋转双层石墨烯具有线性的电子能量色散关系, 但其费米速度随着旋转角度的减小而降低. 进一步研究其电子能带结构发现, 不同旋转角度的双层石墨烯在M点可能会出现大小不同的的带隙, 而这些能隙会增强双层石墨烯的拉曼模强度, 并由拉曼光谱实验所证实. 通过对比双层石墨烯的晶体结构和电子态密度, 发现M点处带隙来自于晶体结构中的“类AB堆垛区”. 关键词： 旋转双层石墨烯 第一性原理 紧束缚 电子结构     

Si面4H-SiC衬底上外延石墨烯近平衡态制备

SiC热解法是制备大面积、高质量石墨烯的理想选择之一.外延石墨烯的晶体质量仍是制约其应用的关键因素之一.本文通过SiC热解法在4H-SiC(0001)衬底上制备单层外延石墨烯.通过引入氩气惰性气氛和硅蒸气,使SiC衬底表面的Si原子升华与返回概率接近平衡,外延石墨烯生长速率大大减慢,单层石墨烯的生长时间从15 min延长至75 min.测试分析表明,生长速率减慢,外延石墨烯中缺陷减少,晶体质量提高,使得外延石墨烯的电性能都得到改善,单层外延石墨烯的最高载流子迁移率达到1200 cm2/V·s,方阻604?/.以上结果表明,控制生长气氛,减慢生长速率是实现高质量外延石墨烯的可行途径之一.     

Layer‐by‐layer AuCl3 doping of stacked graphene films

We investigated the effect of layer‐by‐layer AuCl₃ doping on the electrical and optical properties of stacked graphene films. Graphene grown by the chemical‐vapor deposition method on a Cu‐foil was chemically doped by AuCl₃ solution with a concentration of 20 mM. Eight different configurations were prepared and analyzed by using four‐point probe measurements, optical transmittance measurements, scanning electron microscopy, and micro‐Raman spectroscopy to compare the optical and electrical characteristics of the different graphene samples. In our study, the top‐layer doping method was very effective because better performances considering both sheet resistance and optical transmittance were observed from the configurations with the top‐layer doped. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Chemical vapor deposition of graphene on silver foil as a tarnish‐resistant coating

Here, we demonstrate the synthesis of graphene on Ag foil by an atmospheric‐pressure (AP) chemical vapor deposition (CVD) process as tarnish‐resistant coating. Synthesis of a continuous graphene film on Ag foil is achieved using the solid camphor as carbon precursor in a gas mixture of Ar and H₂. Tarnishing of the Ag surface through sulfidation is investigated with and without coating of the graphene film. It is observed that the bare Ag surface immediately reacts with sulfur vapor to turn black, whereas graphene coating passivates the Ag surface robustly and thereby restrains the sulfur reaction to preserve from tarnishing. Our findings show that a large‐area graphene film can be effectively grown on Ag surface by a CVD process as a tarnish and corrosion resistance barrier.

     

CuNi binary alloy catalyst for growth of nitrogen‐doped graphene by low pressure chemical vapor deposition

The CuNi binary alloy can be significant as a catalyst for nitrogen‐doped (N‐doped) graphene growth considering controllable solubility of both carbon and nitrogen atoms. Here, we report for the first time the possibility of synthesizing substitutional N‐doped bilayer graphene on the binary alloy catalyst. Raman spectroscopy, atomic force microscopy and transmission electron microscopy analysis confirm the growth of bilayer and few‐layer graphene domains. X‐ray photoelectron spectroscopy analysis shows the presence of around 5.8 at% of nitrogen. Our finding shows that large N‐doped bilayer graphene domains can be synthesized on the CuNi binary alloy.

     

铜表面抗氧化性能与其覆盖石墨烯的层数依赖关系研究

We studied the oxidation resistance of graphene-coated Cu surface and its layer dependence by directly growing monolayer graphene with different multilayer structures coexisted, di-minishing the influence induced by residue and transfer technology. It is found that the Cu surface coated with the monolayer graphene demonstrate tremendous difference in oxidation pattern and oxidation rate, compared to that coated with the bilayer graphene, which is considered to be originated from the strain-induced linear oxidation channel in monolayer graphene and the intersection of easily-oxidized directions in each layer of bilayer graphene, respectively. We reveal that the defects on the graphene basal plane but not the boundaries are the main oxidation channel for Cu surface under graphene protection. Our finding indi-cates that compared to putting forth efforts to improve the quality of monolayer graphene by reducing defects, depositing multilayer graphene directly on metal is a simple and effective way to enhance the oxidation resistance of graphene-coated metals.     

Resonant surface enhanced Raman scattering by ultra thin Langmuir-Blodgett polydiacetylene polymer films

Using resonant Raman scattering and surface enhanced Raman scattering techniques, changes in the structural and electronic properties of Langmuir-Blodgett (L-B) polydiacetylene films were observed as film thicknesses were increased from one monolayer (or one bilayer) to several bilayers. The L-B films, starting with a single monolayer (or one bilayer) in a disordered “red” phase, were found to change into a mixed phase (ordered “blue” and disordered “red”) as one or more additional bilayers were deposited. This is the first observation of a “disorder to order” transformation in a L-B film. The observed effect is attributed to the ordering brought about by interactions between the initial and subsequent L-B PDA bilayers.