Geometry and temperature effects of the interfacial thermal conductance in copper- and nickel-graphene nanocomposites

Graphene has excellent mechanical, electrical and thermal properties. Recently, graphene-metal composites have been proposed as a means to combine the properties of metals with those of graphene, leading to mechanically, electrically and thermally functional materials. The understanding of metal-graphene nanocomposites is of critical importance in developing next-generation electrical, thermal and energy devices, but we currently lack a fundamental understanding of how their geometry and composition control their thermal properties. Here we report a series of atomistic simulations, aimed at assessing the geometry and temperature effects of the thermal interface conductance for copper- and nickel-graphene nanocomposites. We find that copper-graphene and nickel-graphene nanocomposites have similar thermal interface conductances, but that both cases show a strong performance dependence on the number of graphene layers between metal phases. Single-graphene-layer nanocomposites have the highest thermal interface conductance, approaching ~500 MW m(-2) K(-1). The thermal interface conductance reduces to half this value in metal-bilayer graphene nanocomposites, and for more than three layers of graphene the thermal interface conductances further reduces to ~100 MW m(-2) K(-1) and becomes independent with respect to the number of layers of graphene. This dependence is attributed to the relatively stronger bonding between the metal and graphene layer, and relatively weaker bonding between graphene layers. Our results suggest that designs combining metal with single graphene layers provide the best thermal properties.     

Intercalation of metals and silicon at the interface of epitaxial graphene and its substrates

Intercalations of metals and silicon between epitaxial graphene and its substrates are reviewed. For metal intercala- tion, seven different metals have been successfully intercalated at the interface of graphene/Ru（O001） and form different intercalated structures. Meanwhile, graphene maintains its original high quality after the intercalation and shows features of weakened interaction with the substrate. For silicon intercalation, two systems, graphene on Ru（O001） and on Ir（l I 1）, have been investigated. In both cases, graphene preserves its high quality and regains its original superlative properties after the silicon intercalation. More importantly, we demonstrate that thicker silicon layers can be intercalated at the interface, which allows the atomic control of the distance between graphene and the metal substrates. These results show the great potential of the intercalation method as a non-damaging approach to decouple epitaxial graphene from its substrates and even form a dielectric layer for future electronic applications.     

掺杂对金属-MoS_2界面性质调制的第一性原理研究

采用基于密度泛函理论的第一性原理赝势平面波方法,计算了卤族元素掺杂对金属-MoS_2界面性质的影响,包括缺陷形成能、电子能带结构、差分电荷密度以及电荷布居分布.计算结果表明:卤族元素原子倾向于占据单层MoS_2表面的S原子位置;对于单层MoS_2而言,卤族元素的掺杂将在禁带中引入杂质能级以及导致费米能级位置的移动.对于金属-MoS_2界面体系,结合Schottky-Mott模型,证明了卤族元素的掺杂可以有效地调制金属-MoS_2界面间的肖特基势垒高度.发现F和Cl原子的掺杂将会降低体系的肖特基势垒高度.相比之下,Br和I原子的掺杂却增大了体系的肖特基势垒高度.通过差分电荷密度和布居分布的分析,阐明了肖特基势垒高度的被调制是因为电荷转移形成的界面偶极矩的作用导致.研究结果解释了相关实验现象,并给二维材料的器件化应用提供了调节手段.     

Intercalation of germanium oxide beneath large-area and high-quality epitaxial graphene on Ir(111) substrate

Epitaxial growth on transition metal surfaces is an effective way to prepare large-area and high-quality graphene.However,the strong interaction between graphene and metal substrates suppresses the intrinsic excellent properties of graphene and the conductive metal substrates also hinder its applications in electronics.Here we demonstrate the decoupling of graphene from metal substrates by germanium oxide intercalation.Germanium is firstly intercalated into the interface between graphene and Ir(111) substrate.Then oxygen is subsequently intercalated,leading to the formation of a GeO_x layer,which is confirmed by x-ray photoelectron spectroscopy.Low-energy electron diffraction and scanning tunneling microscopy studies show intact carbon lattice of graphene after the GeO_x intercalation.Raman characterizations reveal that the intercalated layer effectively decouples graphene from the Ir substrate.The transport measurements demonstrate that the GeO_x layer can act as a tunneling barrier in the fabricated large-area high-quality vertical graphene/GeO_x/Ir heterostructure.     

Self-assembly of metal–organic frameworks and graphene oxide as precursors for lithium-ion battery applications

We fabricated composites of Fe₂O₃/reduced graphene oxide as lithium-ion batteries anode material with controlled structures by employing self-assembly of metal–organic frameworks (MOFs) and polymer-functionalized graphene oxide as precursors. By electrostatic interaction, the negatively charged MOFs, Prussian Blue (PB), are assembled on poly(diallyldimethylammonium chloride) (PDDA)-functionalized graphene oxide (positive charge). Then the PB cubes become FeOOH nanosheets when treated with sodium hydroxide. Upon further annealing, the FeOOH nanosheets transform to Fe₂O₃ nanoparticles while the graphene oxide become reduced graphene oxide simultaneously. It was found that the composites have good performance as anode of lithium-ion battery. This work shows a new way for self-assembling MOFs and 2D materials.     

Density functional theory studies of interactions of graphene with its environment: Substrate,gate dielectric and edge effects

This paper reviews the theoretical work undertaken using density functional theory (DFT) to explore graphene's interactions with its surroundings. We look at the impact of substrates, gate dielectrics and edge effects on the properties of graphene. In particular, we focus on graphene-on-quartz and graphene-on-alumina systems, exploring their energy spectrum and charge distribution. Silicon-terminated quartz is found to not perturb the linear graphene spectrum. On the other hand, oxygen-terminated quartz and both terminations of alumina bond with graphene, leading to the opening of a band gap. Significant charge transfer is seen between the graphene layer and the oxide in the latter cases. Additionally, we review the work of others regarding the effect of various substrates on the electronic properties of graphene. Confining graphene to form nanoribbons also results in the opening of a band gap. The value of the gap is dependent on the edge properties as well as width of the nanoribbon.     

二硫化钨/石墨烯异质结的界面相互作用及其肖特基调控的理论研究

采用第一性原理方法研究了二硫化钨/石墨烯异质结的界面结合作用以及电子性质,结果表明在二硫化钨/石墨烯异质结中,其界面相互作用是微弱的范德瓦耳斯力.能带计算结果显示异质结中二硫化钨和石墨烯各自的电子性质得到了保留,同时,由于石墨烯的结合作用,二硫化钨呈现出n型半导体.通过改变界面的层间距可以调控二硫化钼/石墨烯异质结的肖特基势垒类型,层间距增大,肖特基将从p型转变为n型接触.三维电荷密度差分图表明,负电荷聚集在二硫化钨附近,正电荷聚集在石墨烯附近,从而在界面处形成内建电场.肖特基势垒变化与界面电荷流动密切相关,平面平均电荷密度差分图显示,随着层间距逐渐增大,界面电荷转移越来越弱,且空间电荷聚集区位置向石墨烯层方向靠近,导致费米能级向上平移,证实了肖特基势垒随着层间距的增加由p型接触向n型转变.本文的研究结果将为二维范德瓦耳斯场效应管的设计与制作提供指导.     

Thermal properties of graphene and multilayer graphene: Applications in thermal interface materials

We review the thermal properties of graphene and multilayer graphene, and discuss graphene’s applications in thermal management of advanced electronics and optoelectronics. A special attention is paid to the use of the liquid-phase-exfoliated graphene and multilayer graphene as the fillers in the thermal interface materials. It has been demonstrated that addition of an optimized mixture of graphene and multilayer graphene to the composites with different matrix materials produces the record-high enhancement of the effective thermal conductivity at the small filler loading fraction (f≤10 vol%). The thermal conductivity enhancement due to the presence of graphene in the composites has been observed for a range of matrix materials used by industry. The hybrid composites where graphene is utilized together with metallic micro- and nanoparticles allow one to tune both the thermal and electrical conductivity of these materials. Theoretical considerations indicate that the graphene-based thermal interface materials can outperform those with carbon nanotubes, metal nanoparticles and other fillers owing to graphene’s geometry, mechanical flexibility and lower Kapitza resistance at the graphene–base material interface.     

石墨烯过渡层对金属/SiC接触肖特基势垒调控的第一性原理研究

由于SiC禁带宽度大,在金属/SiC接触界面难以形成较低的势垒,制备良好的欧姆接触是目前SiC器件研制中的关键技术难题,因此,研究如何降低金属/SiC接触界面的肖特基势垒高度(SBH)非常重要.本文基于密度泛函理论的第一性原理赝势平面波方法,结合平均静电势和局域态密度计算方法,研究了石墨烯作为过渡层对不同金属(Ag,Ti,Cu,Pd,Ni,Pt)/SiC接触的SBH的影响.计算结果表明,单层石墨烯可使金属/SiC接触的SBH降低;当石墨烯为2层时,SBH进一步降低且Ni,Ti接触体系的SBH呈现负值,说明接触界面形成了良好的欧姆接触;当石墨烯层数继续增加,SBH不再有明显变化.通过分析接触界面的差分电荷密度以及局域态密度,SBH降低的机理可能主要是石墨烯C原子饱和了SiC表面的悬挂键并降低了金属诱生能隙态对界面的影响,并且接触界面的石墨烯及其与金属相互作用形成的混合相具有较低的功函数.此外,SiC/石墨烯界面形成的电偶极层也可能有助于势垒降低.     

石墨烯过渡层对金属/SiC接触肖特基势垒调控的第一性原理研究

由于SiC禁带宽度大,在金属/SiC接触界面难以形成较低的势垒,制备良好的欧姆接触是目前SiC器件研制中的关键技术难题,因此,研究如何降低金属/SiC接触界面的肖特基势垒高度(SBH)非常重要.本文基于密度泛函理论的第一性原理赝势平面波方法,结合平均静电势和局域态密度计算方法,研究了石墨烯作为过渡层对不同金属(Ag,Ti,Cu,Pd,Ni,Pt)/SiC接触的SBH的影响.计算结果表明,单层石墨烯可使金属/SiC接触的SBH降低;当石墨烯为2层时,SBH进一步降低且Ni,Ti接触体系的SBH呈现负值,说明接触界面形成了良好的欧姆接触;当石墨烯层数继续增加,SBH不再有明显变化.通过分析接触界面的差分电荷密度以及局域态密度,SBH降低的机理可能主要是石墨烯C原子饱和了SiC表面的悬挂键并降低了金属诱生能隙态对界面的影响,并且接触界面的石墨烯及其与金属相互作用形成的混合相具有较低的功函数.此外,SiC/石墨烯界面形成的电偶极层也可能有助于势垒降低.     

Effect of electrical contact on performance of WSe2 field effect transistors

Two-dimensional (2D) transition metal dichalcogenides (TMDCs) such as tungsten diselenide (WSe₂) have spead many interesting physical properties, which may become ideal candidates to develop new generation electronic and optoelectronic devices. In order to reveal essential features of 2D TMDCs, it is necessary to fabricate high-quality devices with reliable electrical contact. We systematically analyze the effect of graphene and metal contacts on performance of multi-layered WSe₂ field effect transistors (FETs). The temperature-dependent transport characteristics of both devices are tested. Only graphene-contacted WSe₂ FETs are observed with the metal-insulator transition phenomenon which mainly attributes to the ultra-clean contact interface and lowered contact barrier. Further characterization on contact barrier demonstrates that graphene contact enables lower contact barrier with WSe₂ than metal contact, since the Fermi level of graphene can be modulated by the gate bias to match the Fermi level of the channel material. We also analyze the carrier mobility of both devices under different temperatures, revealing that graphene contact can reduce the charge scattering of the device caused by ionized impurities and phonon vibrations in low and room temperature regions, respectively. This work is expected to provide reference for fabricating 2D material devices with decent performances.     

Nonlinear screening and ballistic transport in a graphene p-n junction

We study the charge density distribution, the electric field profile, and the resistance of an electrostatically created lateral p-n junction in graphene. We show that the electric field at the interface of the electron and hole regions is strongly enhanced due to limited screening capacity of Dirac quasiparticles. Accordingly, the junction resistance is lower than estimated in previous literature.     

Effect of spin–orbit coupling on spin transport at graphene/transition metal interface

In spite of large spin coherence length in graphene due to small spin–orbit coupling, the created potential barrier and antiferromagnetic coupling at graphene/transition metal (TM) contacts strongly reduce the spin transport behavior in graphene. Keeping these critical issues in mind in the present work, ferromagnetic (Co, Ni) nanosheets are grown on graphene surface to elucidate the nature of interaction at the graphene/ferromagnetic interface to improve the spin transistor characteristics. Temperature dependent magnetoconductance shows unusual behavior exhibiting giant enhancement in magnetoconductance with increasing temperature. A model based on spin–orbit coupling operated at the graphene/TM interface is proposed to explain this anomalous result. We believe that the device performance can be improved remarkably tuning the spin–orbit coupling at the interface of graphene based spin transistor. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Influence of metal contacts and charge inhomogeneity on transport properties of graphene near the neutrality point

There is an increasing amount of literature concerning electronic properties of graphene close to the neutrality point. Many experiments continue using the two-probe geometry or invasive contacts or do not control samples’ macroscopic homogeneity. We believe that it is helpful to point out some problems related to such measurements. By using experimental examples, we illustrate that the charge inhomogeneity induced by spurious chemical doping or metal contacts can lead to large systematic errors in assessing graphene’s transport properties and, in particular, its minimal conductivity. The problems are most severe in the case of two-probe measurements where the contact resistance is found to strongly vary as a function of gate voltage.     

Multifunctional Hybrids Based on 2D Fluorinated Graphene Oxide and Superparamagnetic Iron Oxide Nanoparticles

Carbon‐based nanomaterials have garnered a lot of attention in the research of yesteryear. Here this study reports a composite based on fluorinated graphene oxide—a multifunctional subsidiary of graphene; and iron oxide nanoparticles as a contrast agent for magnetic resonance imaging (MRI). Extensive structural and functional characterization is carried out to understand composite behavior toward biotoxicity and its performance as a contrast agent. The electron withdrawing fluorine group decreases the charge transfer to iron oxide increasing the magnetic saturation of the composite thus enhancing the contrast. The interaction of paramagnetic and superparamagnetic systems yields a superior contrast agent for MRI and fluorescent imaging.     

Thermal properties of transition-metal dichalcogenide

Beyond graphene, the layered transition metal dichalcogenides(TMDs) have gained considerable attention due to their unique properties. Herein, we review the lattice dynamic and thermal properties of monolayer TMDs, including their phonon dispersion, relaxation time, mean free path(MFP), and thermal conductivities. In particular, the experimental and theoretical studies reveal that the TMDs have relatively low thermal conductivities due to the short phonon group velocity and MFP, which poses a significant challenge for efficient thermal management of TMDs-based devices. Importantly,recent studies have shown that this issue could be largely addressed by connecting TMDs and other materials(such as metal electrode and graphene) with chemical bonds, and a relatively high interfacial thermal conductance(ITC) could be achieved at the covalent bonded interface. The ITC of MoS_2/Au interface with chemical edge contact is more than 10 times higher than that with physical side contact. In this article, we review recent advances in the study of TMD-related ITC.The effects of temperature, interfacial vacancy, contact orientation, and phonon modes on the edge-contacted interface are briefly discussed.     

Auto‐barrier‐thinning effect under rapid anodization of nanoporous alumina membrane

We have developed a rapid non‐steady anodization technique that leads to an in‐situ auto‐thinning of the barrier layer due to a space charge limited condition that modifies the local fields at the interfaces of the Al‐Al₂O₃‐electrolyte ternary system. Unlike steady‐state growth, in this non‐steady case an unequal movement of the boundaries of barrier takes place which etches the electrolyte‐oxide interface more than the oxide grows at the oxide‐metal interface, leading to a thinner barrier layer and favouring its complete removal via wet‐etching process. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of electrode material on impedance spectra of metal-polyethylene structures with carbon nanotubes

The effect of an electrode material on electrical properties of a composite material based on super-high-molecular polyethylene (SHMPE) filled with carbon nanotubes has been studied using impedance spectroscopy. Using the method of replacing the sample by an equivalent electric circuit, it has been found that, depending on the electrode material, a blocking barrier with high active resistance and a space charge region adjacent to it arise in the interface region. It has been shown that the barrier height is controlled by surface electronic states of SHMPE and weakly depends on the electron work function of metal electrodes (Bardeen barrier). The characteristic times of electrical relaxation characterizing bulk and interface regions of the composite under study have been determined.     

铝-金刚石界面电子特性与界面肖特基势垒的杂化密度泛函理论HSE06的研究

宽带隙半导体金刚石具有突出的电学与热学特性,近年来,基于金刚石的高频大功率器件受到广泛关注,对于金属-金刚石肖特基结而言,具有较高的击穿电压和较小的串联电阻,所以金属-金刚石这种金半结具有非常好的发展前景.本文通过第一性原理方法去研究金属铝-金刚石界面电子特性与肖特基势垒的高度.界面附近原子轨道的投影态密度的计算表明:金属诱导带隙态会在金刚石一侧产生,并且具有典型的局域化特征,同时可以发现电子电荷转移使得Fermi能级在金刚石一侧有所提升.电子电荷在界面的重新分布促使界面形成新的化学键,使得金属铝-氢化金刚石形成稳定的金半结.特别地,我们通过计算平均静电势的方法得到金属铝-氢化金刚石界面的势垒高度为1.03 eV,该值与金属诱导带隙态唯像模型计算的结果非常接近,也与实验值符合得很好.本文的研究可为金属-金刚石肖特基结二极管的研究奠定理论基础,也可为金刚石基金半结大功率器件的研究提供理论参考.     

Thermodynamic approach to enhance the dispersion of graphene in epoxy matrix and its effect on mechanical and thermal properties of epoxy nanocomposites

Graphene-reinforced polymer nanocomposites are under intense investigation in recent years. In this work, graphene nanosheets have been prepared using chemical reduction method of graphene oxide. Graphene-reinforced epoxy nanocomposites show an enhancement in mechanical and thermal properties at 0.05 wt.% of graphene in epoxy matrix. Modification of graphene with polyvinylpyrrolidone (PVP) shows the significant enhancement in mechanical and thermal properties of epoxy nanocomposites. PVP-modified graphene nanosheets reduces the gap of enthalpic and entropic penalties and facilitates improved dispersion of graphene in epoxy matrix. In addition, enhanced dispersion of PVP-modified graphene in epoxy matrix results in better load transfer across graphene–epoxy interface. Glass transition temperature (T_g) of PVP-modified graphene epoxy nanocomposites increases as compared to pure epoxy because there exist an interaction between epoxy and PVP. Fractography study reveals the localized ductile fracture.