Superior thermal conductivity of single-layer graphene

We report the measurement of the thermal conductivity of a suspended single-layer graphene. The room temperature values of the thermal conductivity in the range approximately (4.84+/-0.44)x10(3) to (5.30+/-0.48)x10(3) W/mK were extracted for a single-layer graphene from the dependence of the Raman G peak frequency on the excitation laser power and independently measured G peak temperature coefficient. The extremely high value of the thermal conductivity suggests that graphene can outperform carbon nanotubes in heat conduction. The superb thermal conduction property of graphene is beneficial for the proposed electronic applications and establishes graphene as an excellent material for thermal management.     

A facile approach to the synthesis of graphene nanosheets under ultra-low exfoliation temperature

High specific surface area graphene nanosheets have been obtained from graphite oxide by using an effective modified exfoliation method under vacuum, the exfoliation temperature (135 degrees C) is much lower than that conventionally applied (1050 degrees C) to obtain monolayer graphene sheets via rapid thermal shock. These products have fluffy and highly porous structure and with a lateral size typically of a few micrometers. Transmission electron microscopy (TEM) observation shows that it looks like a wrinkled transparent ultrathin film consisting of single or few-layer graphene sheets, and their Brunauer-Emmett-Teller surface area is as large as 750 m2/g. Simultaneously, X-ray photoelectron spectroscopy analysis revealed that considerable amount of oxygen-containing groups (C/O ratio, 5:1) retained on the graphene sheets after exfoliation process, which would provide convenience for further modification of the surface properties and chemistry of graphene sheets. This work offers a facile and scalable approach to fabricate graphene oxide and opens up a new vista of various potential applications electronics and composite materials.     

Spinodal decomposition of mono- to few-layer graphene on Ni substrates at low temperature

Mono to few-layer graphene were prepared on pre-annealed polycrystalline nickel substrates by chemical vapor deposition at a relatively low temperature of 800 degrees C using fast cooling rate. It was observed that the reduced solubility of Carbon in Ni at low temperature and an optimum gas mixing ratio (CH4:H2 = 60/80 (sccm)) can be used to synthesize mano-layer graphene that covers about 100 microm2 area. The number of graphene layers strongly depends upon the hydrogen and methane flow rates. An increase in the methane flow is found to increase the growth density of the single-layer graphene. The number of graphene layers was identified from micro-Raman spectra. The thinnest areas containing mono-layer graphene formed at small Ni grains surrounded by large Ni Grains can be explained in terms of Spinodal decomposition. Scanning tunneling microscopy observations of the graphene samples indicate that the graphene structure exhibits no defects, and extremely symmetry hexagon carbon at flat graphene surface is observed.     

低温一步制备氧化石墨烯及微波还原研究

以天然鳞片石墨为原料,通过低温一步氧化制备氧化石墨烯,经微波热还原得到低缺陷的还原氧化石墨烯。讨论了低温氧化过程中氧化剂用量、氧化时间对氧化石墨烯层间距、氧化程度的影响。结果表明:在高锰酸钾与天然鳞片石墨的质量比为1∶3,氧化温度为0℃,氧化时间为48h的条件下,制备出碳氧原子比为1.98、高C—O结构、低缺陷结构( I D∶ I G=0.63)的氧化石墨烯,避免了Hummers制备过程中由于CO 2的形成导致六元环断裂以及碳原子的缺失而使得氧化石墨烯的缺陷增加;经微波热还原后,得到的还原氧化石墨烯的两点平均缺陷距离 L D=12nm,缺陷密度 n D=2.21×10 11 cm -2 , I D∶ I G仅为0.85(Γ G=32.1cm -1 ),制备出低缺陷的还原氧化石墨烯。     

Magnetic transitions in graphene derivatives

The magnetic transitions in graphene oxide (GO) have been investigated experimentally. Micron-sized GO flakes exhibit dominant diamagnetism accompanied by weak ferromagnetism at room temperature. However, when the lateral dimensions of GO flakes are reduced from micron-size to nano-size, a clear transition from dominant diamagnetism to ferromagnetism is observed. After reducing the GO chemically or thermally, the dominant magnetic properties are not altered markedly except for the gradual enhancement of ferromagnetic components. In contrast, at 2 K, significant paramagnetism is present in both the micron-sized and nano-sized GO sheets. The effects of different functional groups on magnetic transitions in graphene derivatives have been further investigated using on hydroxyl-, carboxyl-, amino- and thiolfunctionalized graphene. The results reveal that significant diamagnetism with weak ferromagnetism is present at room temperature in all of these functionalized graphene derivatives and the ability of different functional groups to introduce magnetic moments follows the order -SH > -OH > -COOH, -NH₂. Notably, at 5 K, diamagnetism, paramagnetism and ferromagnetism coexist in thiol-, hydroxyland carboxyl-functionalized graphene, while amino-graphene exhibits dominant paramagnetism, analogous to the low-temperature magnetism in GO. These results indicate that diamagnetism, paramagnetism and ferromagnetism can coexist in graphene derivatives and magnetic transitions among the three states can be achieved which depend on edge states, vacancies, chemical doping and the attached functional groups. The results obtained may help settle the current controversy about the magnetism of graphene-related materials.      

聚丙烯腈/石墨烯纳米复合物的制备、表征及其热性能

采用以水和N,N-二甲基甲酰胺的混合溶剂作反应介质的沉淀聚合法制备了聚丙烯腈/石墨烯纳米复合物。利用傅里叶红外光谱(FT-IR)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和广角X射线衍射(XRD)研究了聚丙烯腈/石墨烯复合物的组成、结构、形貌及两组份的相互作用。利用差式扫描量热分析(DSC)研究了聚丙烯腈及纳米复合物的热性能。结果表明,强极性的聚丙烯腈与石墨烯之间存在较强的非共价相互作用;由于石墨烯的加入,聚丙烯腈的玻璃化转变温度提高了30℃;石墨烯添加量为3%(质量分数)时,聚丙烯腈在氮气和空气中的环化反应放热峰值分别提高了3和11℃;石墨烯使聚丙烯腈在热稳定化过程中的环化反应和氧化反应放热峰宽化、缓和。     

Approaching ballistic transport in suspended graphene

The discovery of graphene raises the prospect of a new class of nanoelectronic devices based on the extraordinary physical properties of this one-atom-thick layer of carbon. Unlike two-dimensional electron layers in semiconductors, where the charge carriers become immobile at low densities, the carrier mobility in graphene can remain high, even when their density vanishes at the Dirac point. However, when the graphene sample is supported on an insulating substrate, potential fluctuations induce charge puddles that obscure the Dirac point physics. Here we show that the fluctuations are significantly reduced in suspended graphene samples and we report low-temperature mobility approaching 200,000 cm2 V-1 s-1 for carrier densities below 5 x 109 cm-2. Such values cannot be attained in semiconductors or non-suspended graphene. Moreover, unlike graphene samples supported by a substrate, the conductivity of suspended graphene at the Dirac point is strongly dependent on temperature and approaches ballistic values at liquid helium temperatures. At higher temperatures, above 100 K, we observe the onset of thermally induced long-range scattering.     

Optoelectronic properties of graphene thin films prepared by thermal reduction of graphene oxide

Graphene thin films have been prepared by thermal reduction of graphene oxide. Raising the reduction temperature results in a red-shift of the G peak in Raman spectra. The reduction temperature turns out to strongly affect the morphology of the prepared graphene film. Photoluminescence (PL) results show that the band gap of graphene can be tuned by varying the reduction temperature. The thermal reduction process has been optimized in an effort to minimize the formation of wrinkles/folds on the graphene surface leading to enhanced PL and Raman peak intensities and reduced electrical sheet resistance.     

球状纳米二氧化钛/石墨烯复合材料的合成及导电性能

采用改进的水热法制备二氧化钛/石墨烯(TiO2/G)复合导电材料,并研究水热温度以及石墨烯用量对TiO2/G复合材料导电性的影响。利用傅里叶变换红外(FTIR)光谱、X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)和电化学阻抗谱等测试手段对复合材料的结构,微观形貌以及导电性能进行表征,并确定最佳的水热温度以及石墨烯的最佳添加量。结果表明:石墨烯添加量为5%(质量分数),水热温度为160℃,TiO2/G复合材料的导电性最佳,其电阻率为13.46Ω·cm。复合材料中TiO2纳米颗粒为球状的锐钛矿相,直径为100~200nm左右,且均匀生长在石墨烯片层表面。其中,TiO2纳米颗粒生长于石墨烯片层上,有效地阻止石墨烯片层的聚集,有利于石墨烯片层间形成导电网络,提高电子迁移效率,赋予二氧化钛复合材料优异的导电性能。     

Temperature-dependent near-infrared spectra of bovine serum albumin in aqueous solutions: spectral analysis by principal component analysis and evolving factor analysis

Fourier transform near-infrared (FT-NIR) spectra have been measured for bovine serum albumin (BSA) in an aqueous solution (pH 6.8) with a concentration of 5.0 wt% over a temperature range of 45-85 degrees C. Not only conventional spectral analysis methods, such as second-derivative spectra and difference spectra, but also chemometrics, such as principal component analysis (PCA) and evolving factor analysis (EFA), have been employed to analyze the temperature-dependent NIR spectra in the 7500-5500 and 4900-4200 cm-1 regions of the BSA aqueous solution. Intensity changes of bands in the 7200-6600 cm-1 and 4650-4500 cm-1 regions in the difference spectra indicate variations of the hydration and secondary structure of BSA in the aqueous solution, respectively. The plot of a band intensity at 7080 cm-1 in the different spectra shows a clear turning point at 63 degrees C, revealing that a significant change in the hydration occurs at about 63 degrees C. The forward and backward eigenvalues (EVs) from EFA suggest that marked changes in the hydration and secondary structure of BSA take place in the temperature ranges of 61-65 degrees C and 59-63 degrees C, respectively. In addition, the temperature of 71 degrees C marked in the EFA plots may correspond to the onset temperature of increase in the intermolecular beta-sheet structure.     

Functionalized graphene sheets for polymer nanocomposites

Polymer-based composites were heralded in the 1960s as a new paradigm for materials. By dispersing strong, highly stiff fibres in a polymer matrix, high-performance lightweight composites could be developed and tailored to individual applications. Today we stand at a similar threshold in the realm of polymer nanocomposites with the promise of strong, durable, multifunctional materials with low nanofiller content. However, the cost of nanoparticles, their availability and the challenges that remain to achieve good dispersion pose significant obstacles to these goals. Here, we report the creation of polymer nanocomposites with functionalized graphene sheets, which overcome these obstacles and provide superb polymer-particle interactions. An unprecedented shift in glass transition temperature of over 40 degrees C is obtained for poly(acrylonitrile) at 1 wt% functionalized graphene sheet, and with only 0.05 wt% functionalized graphene sheet in poly(methyl methacrylate) there is an improvement of nearly 30 degrees C. Modulus, ultimate strength and thermal stability follow a similar trend, with values for functionalized graphene sheet- poly(methyl methacrylate) rivaling those for single-walled carbon nanotube-poly(methyl methacrylate) composites.     

Synthesis of graphene on SiC substrate via Ni-silicidation reactions

In this work, the features of graphene layers are studied with the aim of preparing the thinnest layers possible. The graphene layers were prepared by the annealing of Ni/SiC structures. The main advantage of this process is a relatively low temperature compared with the method of graphene epitaxial growth on SiC and short annealing times compared with the chemical vapor deposition method. We prepared graphene layers from several Ni/SiC structures in which the Ni layer thickness ranged from 1 to 200 nm. The parameters of the annealing process (temperature, rate of temperature increase, annealing time) were modified during the experiments. The formed graphene layers were analyzed by means of Raman spectroscopy. From the spectra, the basic parameters of graphene, such as the number of carbon layers and crystallinity, were determined. The annealing of the Ni(200 nm)/SiC structure at 1080 °C for 10 s, produced graphene in the form of 3-4 carbon monolayers. The value was verified by X-ray Photoelectron Spectroscopy (XPS). Good agreement was achieved in the results obtained using Raman spectroscopy and XPS.     

Structure and chemical reactivity of lithium-doped graphene on hydrogen-saturated silicon carbide

Herein, we studied the structure and hydrogenation of graphene supported on hydrogen-terminated SiC, with intercalated Li atoms. Strong nonbonded interactions occur between graphene and the Si–H groups. The latter were found to be significantly augmented by the intercalation of Li atoms, which enhanced the SiH::pi interactions. Although the electronic structure of graphene did not experience significant changes when supported on hydrogen-terminated SiC, a small gap of 0.04 eV was computed at the HSEH1PBE/6-31G* level. The clustering of Li atoms over graphene was prevented by the SiC support. A significant enhancement of reactivity could be corroborated due to the presence of intercalated Li atoms, given that the C–H binding energy was increased by almost 1 eV with respect to pristine graphene. We expect that hydrogen-terminated SiC with intercalated Li atoms can be used to enhance the chemical reactivity of graphene, given that it strongly interacts with graphene but does not compete for the electrons donated by Li.     

Ion implantation assisted synthesis of graphene on various dielectric substrates

Direct synthesis of high-quality graphene on dielectric substrates is of great importance for the application of graphene-based electronics and optoelectronics. However, high-quality and uniform graphene film growth on dielectric substrates has proven challenging due to limited catalytic ability of dielectric substrates. Here, by employing a Cu ion implantation assisted method, high-quality and uniform graphene can be directly formed on various dielectric substrates including SiO2/Si, quartz glass, and sapphire substrates. The growth rate of graphene on the dielectric substrates was significantly improved due to the catalysis of Cu. Moreover, during the graphene growth process, the Cu atoms gradually evaporated away without involving any metal contamination. Furthermore, an interesting growth behavior of graphene on sapphire substrate was observed, and the results show the graphene domains growth tends to grow along the sapphire flat terraces. The ion implantation assisted approach could open up a new pathway for the direct synthesis of graphene and promote the potential application of graphene in electronics.     

In situ synthesis of silver/chemically reduced graphene nanocomposite and its use for low temperature conductive paste

In this work, we succeeded in the synthesis of Ag/chemically reduced graphene (Ag/G) nanocomposite by a facile in situ one-pot solvothermal route. X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectra and Fourier transform infrared spectroscopy results revealed the formation of Ag and the reduction of graphite oxide to graphene during the one-pot process. Scanning electron microscopy observation indicated that spherical Ag particles with a size less than 100 nm are wrapped by graphene. The Ag/G nanocomposite was used in a low temperature conductive paste. Thermal analysis was conducted to determine the proper curing process of the Ag/G conductive paste. The Ag/G conductive paste that contains 0.6 wt% graphene exhibits low sheet resistance (22 mΩ/sq/25 µm) and good stability after cured at 150?°C for 30 min, which made us believe that the Ag/G nanocomposite is a promising candidate for conductive paste.     

Heat conduction across monolayer and few-layer graphenes

We report the thermal conductance G of Au/Ti/graphene/SiO(2) interfaces (graphene layers 1 ≤ n ≤ 10) typical of graphene transistor contacts. We find G ≈ 25 MW m(-2) K(-1) at room temperature, four times smaller than the thermal conductance of a Au/Ti/SiO(2) interface, even when n = 1. We attribute this reduction to the thermal resistance of Au/Ti/graphene and graphene/SiO(2) interfaces acting in series. The temperature dependence of G from 50 ≤ T ≤ 500 K also indicates that heat is predominantly carried by phonons through these interfaces. Our findings suggest that metal contacts can limit not only electrical transport but also thermal dissipation from submicrometer graphene devices.     

Observation of Raman g-peak split for graphene nanoribbons with hydrogen-terminated zigzag edges

Raman scattering of individual hydrogen-terminated zigzag-edged graphene nanoribbons (Z-GNRs) was studied with focus on the G-peak. In addition to the bulk graphene G-peak appearing at ～1594 cm(-1) (G(+)), an edge-related G-peak at ～1583 cm(-1) (G(-)) was observed for Z-GNRs. This additional Raman vibrational mode originates from the zigzag edges where localized metallic edge states are present. The relative intensity ratio G(-)/G(+) displays a strong dependence on the ribbon width (W). It increases gradually with decreasing W, and the G(+) finally vanishes at W = 5(±3) nm. Polarized Raman scattering was also employed to confirm the four-fold symmetry of the split TO modes, and the results are in good agreement with previous theoretical predictions. Our work offers the first direct experimental evidence to confirm the validity of predicted Raman scattering of GNRs.     

Organic photovoltaic devices based on an acceptor of solution-processable functionalized graphene

We prepared the exfoliation of graphite, which was necessary for the production of graphene sheets that are desirable for the fabrication of nano-composites. Then a Solution-Processable Functionalized Graphene (SPFGraphene) with functionalization groups doped with P3HT hybrid thin film-based organic photovoltaic cells (OPVCs) was systematically identified using a general device structure of, ITO/PEDOT:PSS/P3HT:SPFGraphene/LiF/Al. The effect of annealing on the photoelectric properties of the SPFGraphene was analyzed by Fourier transform infrared FT-IR spectroscopy and solar cell performance. After treatment at different annealing temperatures, with an increase in the SPFGraphene content, the short-circuit current density J(SC) and power conversion efficiency PCE of the hybrid devices increased first, reaching the peak efficiency for the 10 wt% SPFGraphene content, and then decreased. After annealing at 160 degrees C, the device containing 10 wt% SPFGraphene showed the open-circuit voltage V(OC) of 0.73 V, the J(SC) value of 3.98 mA cm(-2), fill factor (FF) value of 0.36, the PCE value of 1.046%. After thermal annealing at 210 degrees C, with the removal of the functional groups and recovery of the pi-conjugated areas, the conductivity of the graphene sheet and the charge carrier-transport mobility increased greatly, the J(SC) value of the 10 wt% SPFGraphene content device increased to 4.2 mA cm(-2), the V(OC) value decreased to 0.59 V, which may be attributed to the altered work-function value of the functionalized graphene and low quasi-Fermi levels for electrons and holes, the FF value was 0.27, and the PCE was 0.669%, which is lower than the former one. The results indicated that annealing at the appropriate temperature can improve the device performance greatly, and the functionalized graphene is expected to be a competitive candidate in organic photovoltaic applications because it is soluble, cheap, easily prepared, stable, and inert against the ambient conditions.     

Micro-Raman densimeter for CO2 inclusions in mantle-derived minerals

We investigated the applicability of Raman microprobe spectroscopy for determining the density of CO2 in fluid inclusions in minerals of mantle-derived xenolith samples. A separation (delta) between two Raman bands of CO2 due to Fermi resonance can be a reliable densimeter for CO2 fluid. The relationship between the density of CO2 (g/cm3) and delta (cm-1) can be expressed as: d = -0.03238697 delta 3 + 10.08428 delta 2 - 1046.189 delta + 36163.67. This equation was obtained from the Raman data on CO2 fluid with densities from 0.1 to 1.21 g/cm3, including super critical fluids at 58-59 degrees C. The delta value was constant with increasing temperature from room temperature to 200 degrees C. This indicates that the Raman densimeter is not affected by a possible rise in temperature, an artifact induced by the high flux of the incident laser. The minimum size of measurable inclusions is 1 micron, and the precision in the determination of delta is 0.1 cm-1, corresponding to 0.02 g/cm3 for inclusions of 1 micron in size. The precision can be better for larger inclusions. The micro-Raman densimeter can determine the density of CO2 fluid inclusions over a wide range. In particular, densities of gas and mixtures of gas and liquid phases, which cannot be measured by microthermometry, can be determined.     

Monitoring dopants by Raman scattering in an electrochemically top-gated graphene transistor

The recent discovery of graphene has led to many advances in two-dimensional physics and devices. The graphene devices fabricated so far have relied on SiO(2) back gating. Electrochemical top gating is widely used for polymer transistors, and has also been successfully applied to carbon nanotubes. Here we demonstrate a top-gated graphene transistor that is able to reach doping levels of up to 5x1013 cm-2, which is much higher than those previously reported. Such high doping levels are possible because the nanometre-thick Debye layer in the solid polymer electrolyte gate provides a much higher gate capacitance than the commonly used SiO(2) back gate, which is usually about 300 nm thick. In situ Raman measurements monitor the doping. The G peak stiffens and sharpens for both electron and hole doping, but the 2D peak shows a different response to holes and electrons. The ratio of the intensities of the G and 2D peaks shows a strong dependence on doping, making it a sensitive parameter to monitor the doping.