金属衬底上石墨烯的红外近场光学

对石墨烯/铜体系开展了系统性的近场光学实验研究,成功观测到了区别于铜衬底的、来自石墨烯的近场光学响应信号,发现在表面台阶几何参数相同的铜衬底上的不同石墨烯样品表现出了截然不同的近场光学响应.     

Itinerant electron theory of transition metal compounds of mixed valency: La1−xSrxMnO3

We use a simplified model to calculate the electronic band structure of compounds of the type of La_1?xSr_xMnO₃. The model includes two nonequivalent sites for the transition metal ions as well as strong Coulomb and exchange interactions between d electrons. Using the resulting band structure we discuss the correlation between magnetic order and conductivity in these compounds.     

Electrical properties of organic field effect transistors with thin graphite/metal electrode directly grown by ICP-CVD at low temperatures

The high contact resistance of organic thin film transistors (OTFTs), due to the work function difference between metal electrode and organic channel, seriously decreases the electrical properties. Graphene electrode could reduce the contact resistance and improve the electrical performance of OTFTs. However, the high chemical vapor deposition (CVD) temperature (900–1000 °C) limits the available OTFT substrate in the case of direct graphene growth on S/D metal electrodes. Furthermore, the application of a transferred graphene electrode induces significant problems due to the transfer process. In this work, thin graphite sheet was directly grown on a metal electrode by the inductively coupled plasma-chemical vapor deposition (ICP-CVD) method at as low temperature as 400, 500 °C. We show that OFETs with thin graphite sheet/metal, grown at 400, 500 °C, exhibit much lower contact resistance than OFETs with metal-only electrode.     

金属衬底上高质量大面积石墨烯的插层及其机制

石墨烯作为一种新型二维材料,因其优异的性质,在科学和应用领域具有非常重要的意义.而其超高的载流子迁移率、室温量子霍尔效应等,使其在信息器件领域备受关注.如何获得高质量并且与当代硅基工艺兼容的石墨烯功能器件,是未来将石墨烯应用于电子学领域的关键.近年来,研究人员发展了一种在外延石墨烯和金属衬底之间实现硅插层的技术,将金属表面外延石墨烯高质量、大面积的特点与当代硅基工艺结合起来,实现了无需转移且无损地将高质量石墨烯置于半导体之上.通过系统的实验研究并结合理论计算,揭示了插层过程包含四个主要阶段:诱导产生缺陷、异质原子插层、石墨烯自我修复和异质原子扩散成膜,并证实了这一插层机制的普适性.拉曼和角分辨光电子能谱实验结果表明,插层后的石墨烯恢复了本征特性,接近自由状态.此外,还实现了多种单质元素的插层.不同种类的原子形成不同的插层结构,从而构成了多种石墨烯/插层异质结.这为调控石墨烯的性质提供了实验基础,也展现了该插层技术的普适性.     

First-principles study on current through a single π conjugate molecule for analysis of carrier injection through an organic/metal interface

We have studied current flow through a single π conjugate molecule weakly adsorbed to, and sandwiched between, two electrodes, focusing specifically on carrier injection through an organic/metal interface. This is the first calculation to investigate the effects of the orientation of the molecule and the electrode material on current using a first-principles method: in the past, most calculations of current were based on the assumption of covalent bonding of a molecule to electrodes. We modeled two systems in which a naphthalene molecule is sandwiched between gold (Au) or aluminum (Al) electrodes. First, in both systems, the current through the molecule depends on the orientation of the molecule. This indicates that electrons mainly transfer through the π channel, which is the overlap between the molecular π orbital and the electrode orbital. Next, the current in the Au-naphthalene-Au system is higher than that in the Al-naphthalene-Al system. This shows that Au is more suitable as an electrode material than Al. Therefore, the orientation of the molecule at an organic/metal interface and the materials comprising the electrodes play a key role in carrier injection through the interface.     

二硫化钼/石墨烯异质结的界面结合作用及其对带边电位影响的理论研究

采用基于色散修正的平面波超软赝势方法研究了二硫化钼/石墨烯异质结的界面结合作用及其对电荷分布和带边电位的影响.研究表明二硫化钼与石墨烯之间可以形成范德瓦耳斯力结合的稳定堆叠结构.通过能带结构计算,发现二硫化钼与石墨烯的耦合导致二硫化钼成为n型半导体,石墨烯转变成小带隙的p型体系.并通过电子密度差分图证实了界面内二硫化钼附近聚集负电荷,石墨烯附近聚集正电荷,界面内形成的内建电场可以抑制光生电子-空穴对的复合.石墨烯的引入可以调制二硫化钼的能带,使其导带底上移至-0.31 eV,提高了光生电子还原能力,有利于光催化还原反应.     

石墨烯与金属的欧姆接触理论研究

石墨烯材料应用于多种电子器件时不可避免地要与金属电极接触,它们之间的接触电阻直接影响了器件的性能.为了揭示影响金属电极与石墨烯间接触电阻的因素,提出有效地抑制这些影响的措施,本文建立了一种求解接触电阻的物理模型,将载流子的输运分为金属与正下方石墨烯之间、正下方石墨烯与邻近石墨烯之间的两个过程,分别研究各个过程的输运概率;结合金属电极与石墨烯接触对载流子分布的影响分析接触电阻,据此分别探讨了金属电极材料、栅极电压、掺杂浓度、金属与石墨烯原子距离等对接触电阻的影响.为验证理论分析结果的正确性,制作了金与石墨烯接触的实验样品,实验测得的接触电阻与理论分析结果符合.理论分析结果表明,可通过选择与石墨烯功函数接近的金属材料,降低二氧化硅层厚度,增加载流子平均自由程,改进金属材料的表面形态使其更光滑,减小金属与石墨烯耦合长度等方法降低石墨烯与金属电极的接触电阻.     

碱金属修饰的多孔石墨烯的储氢性能

基于第一性原理深入研究了碱金属原子(Li,Na,K)修饰的多孔石墨烯(PG)体系的储氢性能,并且通过从头算分子动力学模拟了温度对Li-PG吸附的H2分子稳定性的影响.研究结果表明,PG结构的碳环中心是碱金属原子最稳定的吸附位置,PG单胞最多可以吸附4个碱金属原子,Li原子被束缚最强,金属原子间无团聚的倾向;H2分子通过极化机制吸附在碱金属修饰的PG结构上,每个金属原子周围最多可以稳定地吸附3个H2分子;Li-PG对H2分子的吸附最强(平均吸附能为-0.246 eV/H2),Na-PG对H2分子的吸附较弱(平均吸附能为-0.129 eV/H2),K-PG对H2分子的吸附最弱(平均吸附能为-0.056 eV/H2),不适合用做储氢材料;在不考虑外界压强且温度为300 K的情况下,Li-PG结构可稳定地吸附9个H2分子,储氢量为9.25 wt.%;在400 K时,有7个吸附H2分子脱离Li-PG的束缚,在600-700 K的范围内,吸附H2分子全部脱离了Li-PG体系的束缚.     

Energy band-gap engineering of graphene nanoribbons

We investigate electronic transport in lithographically patterned graphene ribbon structures where the lateral confinement of charge carriers creates an energy gap near the charge neutrality point. Individual graphene layers are contacted with metal electrodes and patterned into ribbons of varying widths and different crystallographic orientations. The temperature dependent conductance measurements show larger energy gaps opening for narrower ribbons. The sizes of these energy gaps are investigated by measuring the conductance in the nonlinear response regime at low temperatures. We find that the energy gap scales inversely with the ribbon width, thus demonstrating the ability to engineer the band gap of graphene nanostructures by lithographic processes.     

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.     

Transport properties of graphene/metal planar junction

The transport properties of graphene/metal (Cu(111), Al(111), Ag(111), and Au(111)) planar junction are investigated using the first-principles nonequilibrium Green's function method. The planar junction induce second transmission minimum (TM2) below the Fermi level due to the existence of the Dirac point of clamped graphene. Interestingly, no matter the graphene is p- or n-type doped by the metal substrate, the TM2 always locates below the Fermi level. We find that the position of the TM2 is not only determined by the doping effect of metal lead on the graphene, but also influenced by the electrostatic potential of the metal substrate and the work function difference between the clamped and suspended graphene.     

Rashba effect in the graphene/ni(111) system

We report on angle-resolved photoemission studies of the electronic pi states of high-quality epitaxial graphene layers on a Ni(111) surface. In this system the electron binding energy of the pi states shows a strong dependence on the magnetization reversal of the Ni film. The observed extraordinarily large energy shift up to 225 meV of the graphene-derived pi band peak position for opposite magnetization directions is attributed to a manifestation of the Rashba interaction between spin-polarized electrons in the pi band and the large effective electric field at the graphene/Ni interface. Our findings show that an electron spin in the graphene layer can be manipulated in a controlled way and have important implications for graphene-based spintronic devices.     

Long-range exchange bias through a metal spacer

We have theoretically analyzed the long-range exchange bias between a ferromagnet and an antiferromagnet separated by a nonmagnetic metal spacer. The Fermi–Dirac distribution was included in the Ruderman–Kittel–Kasuya–Yosida interaction to study the thermal effects of the conduction electrons, and thus to study the temperature effects and thickness dependence in the trilayer structure. The experimentally observed oscillatory exchange bias through the metal spacer is in good agreement with the calculated results.     

Structural,electronic,and magnetic behaviors of 5d transition metal atom substituted divacancy graphene:A first-principles study

Structural, electronic, and magnetic behaviors of 5d transition metal(TM) atom substituted divacancy(DV) graphene are investigated using first-principles calculations. Different 5d TM atoms(Hf, Ta, W, Re, Os, Ir, and Pt) are embedded in graphene, these impurity atoms replace 2 carbon atoms in the graphene sheet. It is revealed that the charge transfer occurs from 5d TM atoms to the graphene layer. Hf, Ta, and W substituted graphene structures exhibit a finite band gap at high symmetric K-point in their spin up and spin down channels with 0.783 μB, 1.65 μB, and 1.78 μB magnetic moments,respectively. Ir and Pt substituted graphene structures display indirect band gap semiconductor behavior. Interestingly, Os substituted graphene shows direct band gap semiconductor behavior having a band gap of approximately 0.4 e V in their spin up channel with 1.5 μB magnetic moment. Through density of states(DOS) analysis, we can predict that d orbitals of 5d TM atoms could be responsible for introducing ferromagnetism in the graphene layer. We believe that our obtained results provide a new route for potential applications of dilute magnetic semiconductors and half-metals in spintronic devices by employing 5d transition metal atom-doped graphene complexes.     

拓扑石墨烯电极分子器件输运特性

利用密度泛函理论结合非平衡格林函数方法,研究了不同拓扑能带结构的石墨烯电极分子器件输运特性.结果表明器件导通电压与电极禁带宽度正相关,同时器件在输运过程中表现出负微分电阻特性,峰谷电流比可达2697.分析认为器件导通源自于偏压升高过程中两电极能带匹配.器件负微分电阻特性源自于偏压升高过程中两电极能带交错.散射态分析表明,能带匹配后散射态分布较为离域,有利于电子通过器件.能带交错后散射态局域于电极处,表明电子输运受到抑制.     

Formation dynamics of bipolaron in a metal/polymer/metal structure

Charge injection process from metal electrode to a nondegenerate polymer in a metal/ polymer/ metal structure has been investigated by using a nonadiabatic dynamic method. We demonstrate that the dynamical formation of a bipolaron sensitively depends on the strength of applied electric field, the work function of metal electrode, and the contact between the polymer and the electrode. For a given bias applied to one of the electrode (V₀) and coupling between the electrode and the polymer (t^′), such as V₀=0.79 eV and t^′=1 eV, the charge injection process depending on the electric field can be divided into the following three cases: (1) in the absence of the electric field, only one electron tunnels into the polymer to form a polaron near the middle of the polymer chain; (2) at low electric fields, two electrons transfer into the polymer chain to form a bipolaron; (3) at higher electric fields, bipolaron can not be formed in the polymer chain, electrons are transferred from the left electrode to right electrode through the polymer one by one accompanying with small irregular lattice deformations.     

金属纳米薄膜在石墨基底表面的动力学演化

采用分子动力学方法研究了金属Au和Pt纳米薄膜在石墨(烯)基底表面的动力学演化过程,探讨了金属薄膜和石墨(烯)基底间的相互作用对金属纳米薄膜在固态基底表面的去湿以及脱附的动力学演化的影响.研究结果表明,在高温下,相同层数的Au和Pt纳米薄膜在单层石墨基底表面上存在不同的去湿现象,主要表现为厚度较小的Pt纳米薄膜在去湿过程中有纳米空洞形成,而同样厚度的Au薄膜在去湿过程中没有形成空洞.Au和Pt两种金属薄膜在高温下都去湿形成纳米液滴,这些液滴最终都以一定的速度脱离基底.在模拟的薄膜厚度范围内(0.2—2.3 nm),Au和Pt纳米液滴脱离基底的速度随厚度增加表现出不同的变化规律.Pt纳米液滴的脱离速度随薄膜初始厚度的增加先增加后减少,而Au脱离速度随厚度的增加先减少,达到一个临界厚度后脱离速度突然迅速增加.利用薄膜与基底间相互作用的不同导致去湿过程中的黏滞耗散不同,定性分析了这种变化规律的原因.此外,进一步研究还发现金属液滴的脱离时间与薄膜厚度和模拟温度的依赖关系,发现脱离时间随薄膜厚度的增加而增加,随模拟温度的升高而减小.这些研究结果可以为金属镀膜、浮选、表面清洁、器件表面去湿等工业生产过程提供理论指导.     

Electronic transport through zigzag/armchair graphene nanoribbon heterojunctions

The electronic transport properties of a graphene nanoribbon (GNR) are known to be sensitive to its width, edges and defects. We investigate the electronic transport properties of a graphene nanoribbon heterojunction constructed by fusing a zigzag and an armchair graphene nanoribbon (zGNR/aGNR) side by side. First principles results reveal that the heterojunction can be either metallic or semiconducting, depending on the width of the nanoribbons. Intrinsic rectification behaviors have been observed, which are largely sensitive to the connection length between the zGNR and aGNR. The microscopic origins of the rectification behavior have been revealed. We find that the carrier type can alter from electrons to holes with the bias voltage changing from negative to positive; the asymmetrical transmission spectra of electrons and holes induced by the interface defects directly results in the rectification behavior. The results suggest that any methods which can enhance the asymmetry of the transmission spectra between holes and electrons could be used to improve the rectification behavior in the zGNR/aGNR heterojunction. Our findings could be useful for designing graphene based electronic devices.     

金衬底调控单层二硫化钼电子性能的第一性原理研究

基于密度泛函的第一性原理研究了金衬底对单层二硫化钼电子性能的调控作用. 从结合能、能带结构、电子态密度和差分电荷密度四个方面进行了深入研究. 结合能计算确定了硫原子层在界面的排布方式, 并指出这种吸附结构并不稳定. 能带结构分析证实了金衬底与单层二硫化钼形成肖特基接触, 并出现钉扎效应. 电子态密度分析表明金衬底并没有影响硫原子和钼原子之间的共价键, 而是通过调控单层二硫化钼的电子态密度增加其导电率. 差分电荷密度分析表明单层二硫化钼的导电通道可能在界面处产生. 研究结果可对单层二硫化钼晶体管的建模和实验制备提供指导.