还原温度对氧化石墨烯结构及室温下H_2敏感性能的影响

以氧化石墨凝胶制备的氧化石墨烯(GO)溶胶为前驱体,在100—350℃温度下还原获得不同还原程度的还原氧化石墨烯(rGO)样品,并采用旋涂工艺制备还原氧化石墨烯气敏薄膜元件.采用X射线衍射、拉曼光谱、傅里叶变换红外光谱和气敏测试等手段研究还原温度对样品结构、官能团和气敏性能的影响.结果表明:经热还原处理的氧化石墨烯结构向较为有序的类石墨结构转变,还原温度为200℃时,样品处于GO向rGO转变的过渡阶段,还原温度达到250℃时,则表现出还原氧化石墨烯特性;无序程度随还原温度的升高先由0.85增大至1.59,随后减小至1.41,总体呈现增加趋势;氧化石墨烯表面含氧官能团随还原温度的升高逐渐热解失去,不同含氧官能团的失去温度范围不同;热还原氧化石墨烯具有优异的室温H_2敏感性能,随着还原温度的升高,元件灵敏度逐渐减小,响应-恢复时间逐渐增大,最佳灵敏度为88.56%,响应时间为30 s.     

Structural evolution in CVD graphene chemically oxidized by sulphuric acid

The role of sulphuric acid (H₂SO₄) in fabrication graphene oxide besides as intercalant has not been well addressed. In this work, Raman spectroscopy is used to monitor structural evolution in chemical vapor deposition (CVD) graphene chemically oxidized by dilute H₂SO₄. From the analysis of Raman spectra of oxidized graphene, we propose that oxidation first initiates at preexisting defects, and vacancy‐like defects are formed. Following is the radial growth of the vacancy, and oxidation pits appear in graphene. This assumption is further confirmed by atomic force microscope measurement. It is also found that with increase of amounts of defects, G peak is blue shift, and this is explained by defect and hole doping effect. Hole doping in graphene is much stronger at hexagon regions near the oxidation pits. This work helps in understanding the role of H₂SO₄ in fabrication graphene oxide as oxidizer as well as helps in obtaining structure information of graphene oxide. Copyright © 2015 John Wiley & Sons, Ltd.     

Density functional theory study on the adsorption of alkali metal ions with pristine and defected graphene sheet

The graphene-based materials along with the adsorption of alkali metal ions are suitable for energy conversion and storage applications. Hence in the present work, we have investigated the structural and electronic properties of pristine and defected graphene sheet upon the adsorption of alkali metal ions (Li⁺, Na⁺, and K⁺) using density functional theory (DFT) calculations. The presence of vacancies or vacancy defects enhances the adsorption of alkali ions than the pristine sheet. From the obtained results, it is found that the adsorption energy of Li⁺ on the vacancies defected graphene sheet is higher (3.05?eV) than the pristine (2.41?eV) and Stone–Wales (2.50?eV) defected sheets. Moreover, the pore radius of the pristine and defected graphene sheets are less affected by metal ions adsorption. The increase in energy gap upon the adsorption of metal ions is found to be high in the vacancy defected graphene than that of other sheets. The metal ions adsorption in the defective vacancy sheets has high charge transfer from metal ions to the graphene sheet. The bonding characteristic between the metal ions and graphene sheet are analysed using QTAIM analysis. The influence of alkali ions on the electronic properties of the graphene sheet is examined from the Total Density of States (TDOS) and Partial Density of States (PDOS).     

Electrical control of magnetism in oxides

Recent progress in the electrical control of magnetism in oxides,with profound physics and enormous potential applications,is reviewed and illustrated.In the first part,we provide a comprehensive summary of the electrical control of magnetism in the classic multiferroic heterostructures and clarify the various mechanisms lying behind them.The second part focuses on the novel technique of electric double layer gating for driving a significant electronic phase transition in magnetic oxides by a small voltage.In the third part,electric field applied on ordinary dielectric oxide is used to control the magnetic phenomenon originating from charge transfer and orbital reconstruction at the interface between dissimilar correlated oxides.At the end,we analyze the challenges in electrical control of magnetism in oxides,both the mechanisms and practical applications,which will inspire more in-depth research and advance the development in this field.     

Finite temperature effect on mechanical properties of graphene sheets with various grain boundaries

The mechanical properties of graphene sheets with various grain boundaries are studied by molecular dynamics method at finite temperatures.The finite temperature reduces the ultimate strengths of the graphenes with different types of grain boundaries.More interestingly,at high temperatures,the ultimate strengths of the graphene with the zigzagorientation grain boundaries at low tilt angles exhibit different behaviors from those at lower temperatures,which is determined by inner initial stress in grain boundaries.The results indicate that the finite temperature,especially the high one,has a significant effect on the ultimate strength of graphene with grain boundaries,which gives a more in-depth understanding of their mechanical properties and could be useful for potential graphene applications.     

Investigation on thermal conductivity of graphene/Si heterostructure with different defect ratios and sizes

The thermal conductivity (TC) of graphene/Si heterostructures with different defect ratios and sizes was investigated using the molecular dynamics method. As the defect ratio of heterostructure increased, the TC decreased first sharply and then slowly under a high temperature stage. The TC of heterostructure also showed a significant size effect. This phenomenon was explained by phonon dispersion and flip competition. The phonon density of states for the graphene heterostructure with different defect ratios and sizes was obtained to understand the thermal transport mechanism. Analysis showed that with the increase in the defect ratio and when the flexural modes of the heterostructure became weak, the longitudinal and transverse modes gradually dominated the phonon transport. This phenomenon can be explained that the Si atom vibration was harder in the vertical plane than that of graphene. The vibration mode hindered the heat carrier of graphene and affected heat transport to the heterostructure.     

Synthesis and characterization of graphene oxide,reduced graphene oxide and their nanocomposites with polyethylene oxide

This work describes the synthesis of GO, rGO and their nanocomposites with PEO. GO and rGO were prepared by the modified Hummers method and in-situ reduction of GO utilizing green reductant L (+) Ascorbic acid. The nanocomposites were characterized by Fourier-transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), Field emission scanning electron microscopy (FE-SEM), Thermogravimetric Analysis (TGA), and Universal Testing Machine (UTM). FT-IR and XRD confirmed the synthesis of GO and rGO. FE-SEM confirmed the uniformly exfoliated GO and rGO nanosheets in the polymer matrix. Hydrogen bonding was the main interaction mechanism for GO with PEO while no interaction was detected by FT-IR for rGO. Enhanced thermal stability was observed for both GO/PEO and rGO/PEO nanocomposites. The mechanical analysis showed an increase in Young's modulus, tensile strength, and elongation at break for GO/PEO nanocomposites, which is attributed to the homogeneous dispersion and hydrophilic hydrogen bonding interaction of GO with PEO.     

Impact of synthesis routes on the chemical,optical, and electrical properties of graphene oxides and its derivatives

Solution-processed graphene oxides in their reduced forms are prominent prospective functional materials for organic optoelectronics. For graphene oxide synthesis, several methods have been developed, which induce varying properties in their products. However, the dependence of the graphene oxide properties on their synthesis methods has rarely been studied, hindering the selection of the optimum synthesis route for a target application. In this study, we report our study results on the properties of synthesized graphene oxides and their reduced forms created using several synthesis methods, such as the modified Hummers' method, the improved method, and the Staudenmaier's method as well as from two commercial sources, Angstron Material, Inc. and Graphos, Inc. Focusing on the transparent electrode application, the properties of thin films were investigated using UV–visible spectroscopy, Hall measurements, atomic force microscopy, Raman spectroscopy, work function measurements, and X-ray photoelectron spectroscopy. Our results reveal significant morphological, elemental, structural, and optoelectrical property variations among the as-prepared and reduced thin films of graphene oxides by their synthesis methods. In addition, the results show that the graphene oxides synthesized using the modified Hummers' method and the product from Angstron Material, Inc. are the most suitable materials for the transparent electrode application.     

石墨烯低温热膨胀和声子弛豫时间随温度的变化规律

考虑到原子非简谐振动和电子-声子相互作用,用固体物理理论和方法研究了石墨烯格林艾森参量和低温热膨胀系数以及声子弛豫时间随温度的变化规律,探讨了原子非简谐振动项对它们的影响.结果表明:1)在低于室温的温度范围内,石墨烯的热膨胀系数为负值,随着温度的升高,其热膨胀系数的绝对值单调增加,室温热膨胀系数为-3.64×10~(-6)K~(-1);2)简谐近似下的格林艾森参量为零.考虑到非简谐项后,格林艾森参量在1.40-1.42之间并随温度升高而缓慢增大,几乎成线性关系,第二非简谐项对格林艾森参量的影响小于第一非简谐项;3)石墨烯声子弛豫时间随着温度的升高而减小,其中,温度很低(T10 K)时变化很快,此后变化很慢,当温度不太低(T300 K)时,声子弛豫时间与温度几乎成反比关系.     

基于氧化石墨烯的长周期光纤光栅的全光控制

实验验证了一种通过将氧化石墨烯分散液沉积在长周期光纤光栅的全光控制的相关研究。通过外加的垂直泵浦光的作用,氧化石墨烯吸收泵浦光产生热量,改变长周期光纤光栅的包层模式的相位差,由于热膨胀的作用改变了氧化石墨烯所覆盖部分的光栅周期,使得谐振谱发生了移动,其最大调制深度可达10.6 dB,谐振谱最大可红移12.8 nm。通过实验发现,沉积相同浓度氧化石墨烯分散液的次数影响实验结果,通过在相同光栅的相同位置分别沉积三次,发现沉积三次可以在光纤表面获得更加均匀的氧化石墨烯膜,进行了时间响应的测试,其中沉积三次后的长周期光纤光栅的响应速度可达0.61 ms,沉积多次氧化石墨烯分散液可以在光纤表面沉积得更加平整均匀,从而获得更大的导热性能。     

激光烧结石墨烯铜复合材料温度场有限元模拟

在激光烧结石墨烯增强铜基复合材料的过程中,了解瞬时温度场分布对优化工艺参数、控制烧结质量有重要作用。建立了激光烧结预涂在42CrMo基板上的石墨烯铜的混合粉末的有限元模型。研究了激光烧结过程温度场分布,熔池的几何参数以及烧结层与基体的冶金结合宽度。为了验证模拟结果,使用与模拟相同的参数进行了单道激光烧结的实验。研究表明,热传导、热辐射和相变潜热在激光烧结过程的温度场分布中起重要作用。实验结果与模拟结果较为一致。所以可以依据模拟结果预测实验的温度场分布和熔池几何参数,同时也可以据此优化激光烧结参数。     

High temperature characteristics of bilayer epitaxial graphene field-effect transistors on SiC Substrate

In this paper,high temperature direct current(DC) performance of bilayer epitaxial graphene device on SiC substrate is studied in a temperature range from 25℃ to 200℃.At a gate voltage of-8 V(far from Dirac point),the drainsource current decreases obviously with increasing temperature,but it has little change at a gate bias of +8 V(near Dirac point).The competing interactions between scattering and thermal activation are responsible for the different reduction tendencies.Four different kinds of scatterings are taken into account to qualitatively analyze the carrier mobility under different temperatures.The devices exhibit almost unchanged DC performances after high temperature measurements at 200℃ for 5 hours in air ambience,demonstrating the high thermal stabilities of the bilayer epitaxial graphene devices.     

Investigations on the effect of process parameters on the growth of vertically oriented graphene sheet in plasma-enhanced chemical vapour deposition system

A multistage numerical model comprising the plasma kinetics and surface deposition sub-models is developed to study the influence of process parameters, namely, total gas pressure and input plasma power on the plasma chemistry and growth characteristics of vertically oriented graphene sheets (VOGS) grown in the plasma-enhanced chemical vapour deposition system containing the Ar + H₂ + C₂H₂ reactive gas mixture. The spectral and spatial distributions of temperature and number densities, respectively, of plasma species, that is, charged and neutral species in the plasma reactor, are examined using inductively coupled plasma module of COMSOL Multiphysics 5.2 modelling suite. The numerical data from the computational plasma model are fed as the input parameters for the surface deposition model, and from the simulation results, it is found that there is a significant drop in the densities of various plasma species as one goes from the bulk plasma region to the substrate surface. The significant loss of the energetic electrons is observed in the plasma region at high pressure (for constant input power) and low input power (for constant gas pressure). At low pressure, the carbon species generate at higher rates on the catalyst nanoislands surface, thus enhancing the growth and surface density of VOGS. However, it is found that VOGS growth rate increases when input plasma power is raised from 100 to 300 W and decreases with further increase in the plasma power. A good comparison of the model outcomes with the available experimental results confirms the adequacy of the present model.     

Conductance of bilayer graphene nanoribbons with different widths

The electronic and transport properties of bilayer graphene nanoribbons with different width are investigated theoretically by using the tight-binding model. The energy dispersion relations are found to exhibit significant dependence on the interlayer interactions and the geometry of the bilayer graphene nanoribbons. The energy gaps are oscillatory with the upper ribbon displacement. For all four types of bilayer graphene nanoribbons, the bandgaps touch the zero value and exhibit semiconductor–metal transitions. Variations in the electronic structures with the upper ribbon displacement will be reflected in the electrical and thermal conductance. The chemical-potential-dependent electrical and thermal conductances exhibit a stepwise increase and spike behavior. These conductances can be tuned by varying the upper ribbon displacement. The peak and trench structures of the conductance will be stretched out as the temperature rises. In addition, quantum conductance behavior in bilayer graphene nanoribbons can be observed experimentally at temperature below 10 K.     

The influence of annealing temperature on the morphology of graphene islands

We report on temperature-programmed growth of graphene islands on Ru(0001) at annealing temperatures of 700°C,800°C,and 900°C.The sizes of the islands each show a nonlinear increase with the annealing temperature.In 700°C and 800°C annealings,the islands have nearly the same sizes and their ascending edges are embedded in the upper steps of the ruthenium substrate,which is in accordance with the etching growth mode.In 900°C annealing,the islands are much larger and of lower quality,which represents the early stage of Smoluchowski ripening.A longer time annealing at 900°C brings the islands to final equilibrium with an ordered moir’e pattern.Our work provides new details about graphene early growth stages that could facilitate the better control of such a growth to obtain graphene with ideal size and high quality.     

HfO_2-based ferroelectric modulator of terahertz waves with graphene metamaterial

Tunable modulations of terahertz waves in a graphene/ferroelectric-layer/silicon hybrid structure are demonstrated at low bias voltages. The modulation is due to the creation/elimination of an extra barrier in Si layer in response to the polarization in the ferroelectric Si:HfO_2 layer. Considering the good compatibility of HfO_2 with the Si-based semiconductor process, the highly tunable characteristics of the graphene metamaterial device under ferroelectric effect open up new avenues for graphene-based high performance integrated active photonic devices compatible with the silicon technology.     

基于石墨烯编码超构材料的太赫兹波束多功能动态调控

提出了一种基于石墨烯带的太赫兹波段的1 bit编码超构材料,可以实现太赫兹波束的数目、频率、幅度等参数多功能动态调控.该结构由金属薄膜、聚酰亚胺、硅、二氧化硅、石墨烯带组成.通过对石墨烯带施加两种不同的电压,可以实现一定频率范围内相位差接近180?的"0"和"1"数字编码单元,进而构成1 bit动态可控的编码超构材料.全波仿真结果表明,不同序列的编码超构材料能够实现波束数目从单波束、双波束、多波束到宽波束的调控.相同序列的编码超构材料,通过施加石墨烯带的不同电压能够实现宽频段波束频率的偏移.对于000000或者111111周期序列的编码超构材料,通过施加石墨烯带的不同电压还能够实现波束幅度的调控.因此这种基于石墨烯带的编码超构材料为灵活调控太赫兹波提供了一种新的途径,将在雷达隐身、成像、宽带通信等方面具有重要的意义.     

Preparation of graphene on SiC by laser-accelerated pulsed ion beams

Laser-accelerated ion beams (LIBs) have been increasingly applied in the field of material irradiation in recent years due to the unique properties of ultra-short beam duration, extremely high beam current, etc. Here we explore an application of using laser-accelerated ion beams to prepare graphene. The pulsed LIBs produced a great instantaneous beam current and thermal effect on the SiC samples with a shooting frequency of 1 Hz. In the experiment, we controlled the deposition dose by adjusting the number of shootings and the irradiating current by adjusting the distance between the sample and the ion source. During annealing at 1100 ℃, we found that the 190 shots ion beams allowed more carbon atoms to self-assemble into graphene than the 10 shots case. By comparing with the controlled experiment based on ion beams from a traditional ion accelerator, we found that the laser-accelerated ion beams could cause greater damage in a very short time. Significant thermal effect was induced when the irradiation distance was reduced to less than 1 cm, which could make partial SiC self-annealing to prepare graphene dots directly. The special effects of LIBs indicate their vital role to change the structure of the irradiation sample.     

Preparation of graphene on Cu foils by ion implantation with negative carbon clusters

We report on few-layer graphene synthesized on Cu foils by ion implantation using negative carbon cluster ions,followed by annealing at 950?C in vacuum.Raman spectroscopy reveals IG/I2Dvalues varying from 1.55 to 2.38 depending on energy and dose of the cluster ions,indicating formation of multilayer graphene.The measurements show that the samples with more graphene layers have fewer defects.This is interpreted by graphene growth seeded by the first layers formed via outward diffusion of C from the Cu foil,though nonlinear damage and smoothing effects also play a role.Cluster ion implantation overcomes the solubility limit of carbon in Cu,providing a technique for multilayer graphene synthesis.     

The thermal stability of graphene in air investigated by Raman spectroscopy

The thermal stability in air of graphene synthesized by either chemical vapor deposition or mechanical cleavage is studied. It is found that single layer graphene prepared by both methods starts to show defects at ~500 °C, indicated by the appearance of a disorder‐induced Raman D peak. The defects are initially sp³ type and become vacancy like at higher temperature. On the other hand, bilayer graphene shows better thermal stability, and the D peak appears at ~600 °C. These results are quite different from those annealing in vacuum and controlled atmosphere. Raman images show that the defects in chemical vapor deposition graphene are not homogeneous, whereas those in mechanical cleavage graphene are uniformly distributed across the whole sample. The factors that affect the thermal stability of graphene are discussed. Our results could be important for guiding the future electronics process and chemical decoration of graphene. Copyright © 2013 John Wiley & Sons, Ltd.