电场调控双层石墨烯纳米带的电子结构和光学性质

利用基于密度泛函理论的第一性原理方法,研究了外加电场作用下双层AA堆垛的Armchair边缘石墨烯纳米带(BAGNRs)的电子结构和光学性质. BAGNRs具有半导体特性,其带隙随带宽(宽度为4～12个碳原子)的增加而振荡性减小.当施加电场后,BAGNRs的带隙随着电场强度的增加而逐渐减小,带隙越大对电场值的变化越敏感.当电场值为0.5 V/?时,所有BAGNRs的带隙都为零. BAGNRs具有各向异性的光学性质,其介电函数在垂直极化方向为半导体特性,而在平行极化方向为金属特性.在外加电场的作用下,BAGNRs的介电函数、吸收系数、折射系数、反射系数、电子能量损失系数和光电导率,其峰值向低能量区域移动,即产生红移现象.电场增强了能带间的跃迁几率.纳米带宽度对这些光学性质参数具有不同程度的影响.研究结果解释了电场调控BAGNRs光学性质的规律和微观机理.     

外加横向电场作用下石墨烯纳米带电子结构的密度泛函紧束缚计算

采用基于密度泛函理论的紧束缚方法计算研究了外加横向电场对边缘未加氢/加氢钝化的扶手椅型石墨烯纳米带的电子结构及电子布居数的影响.计算结果表明,石墨烯纳米带的能隙变化受其宽带影响.当施加沿其宽度方向的横向外加电场时,纳米带的能带结构及态密度都会产生较大的变化.对于具有半导体性的边缘未加氢纳米带,随着所施加电场强度的增加,会发生半导体-金属的转变.同时,电场也会对能级分布产生显著影响.外加电场导致纳米带内原子上电子布居数分布失去对称性,电场强度越大,其布居数不对称性越明显.边缘加氢钝化可以显著改变纳米带内原子上的布居数分布.     

间二甲苯分子在不同外电场下结构和解离特性研究

间二甲苯是挥发性有机物(VOCs, Volatile Organic Compounds)的关键活性成分,研究其在外电场下的性质十分重要.采用密度泛函理论(DFT),在B3LYP/6-311G++基组水平上对间二甲苯分子进行优化,从分子结构研究了不同外电场(-0.025 a.u.～0.025 a.u.)作用下,间二甲苯分子的总能量,键长,电偶极矩,前线轨道,红外光谱和解离势能面.计算结果表明,沿两甲基中C原子连线方向的电场(-0.025 a.u.～0.025 a.u.)增加时,分子总能量和能隙先增大后减小,电偶极矩先减小后增加.通过计算发现外电场对间二甲苯分子不同键长和不同振动模式的红外光谱的影响均有所不同.间二甲苯分子的解离特性表现为:沿两甲基中C原子连线方向施加强度超过0.047 a. u.的电场时,位于电场增加方向的甲基与苯环之间起连接作用的C-C键断裂.以上计算结果可为利用电场降解间二甲苯提供重要理论参考.     

间二甲苯分子在不同外电场下结构和解离特性研究

间二甲苯是挥发性有机物(VOCs,Volatile Organic Compounds)的关键活性成分，研究其在外电场下的性质十分重要.采用密度泛函理论(DFT)，在B3LYP/6-311G++基组水平上对间二甲苯分子进行优化，从分子结构研究了不同外电场(-0.025 a.u.～0.025 a.u.)作用下，间二甲苯分子的总能量，键长，电偶极矩，前线轨道，红外光谱和解离势能面.计算结果表明，沿两甲基中C原子连线方向的电场(-0.025 a.u.～0.025 a.u.)增加时，分子总能量和能隙先增大后减小，电偶极矩先减小后增加.通过计算发现外电场对间二甲苯分子不同键长和不同振动模式的红外光谱的影响均有所不同.间二甲苯分子的解离特性表现为:沿两甲基中C原子连线方向施加强度超过0.047 a.u.的电场时，位于电场增加方向的甲基与苯环之间起连接作用的C-C键断裂.以上计算结果可为利用电场降解间二甲苯提供重要理论参考．     

LiF分子在外电场中的物理性质研究

本文采用量子力学从头算方法,运用密度泛函B3LYP方法在6-311基组水平上, 对不同外加电场(--0.15---0.15a.u.) 作用下LiF分子基态的稳定电子结构进行了计算,研究了外电场对LiF分子键长、能量、电荷分布、能级分布、能隙及红外光谱的影响规律.结果表明,随着Z方向外电场的增加,分子键长、偶极矩和能隙递增,原子电荷也递增,总能量降低, 频率及其红外强度递减, LiF基态分子势能曲线降低,离解能减小.     

扭转形变对石墨烯吸附O原子电学和光学性质影响的电子理论研究

基于密度泛函理论的第一性原理方法研究了扭转形变对石墨烯吸附O体系结构稳定性、电子结构和光学性质,包括吸附能、带隙、吸收系数及反射率的影响.研究发现,吸附O原子后,距O原子最近的C原子被拔起,导致石墨烯平面发生扭曲.吸附能计算表明,扭转形变使石墨烯吸附O原子体系结构稳定性下降,而扭转程度对结构稳定性影响微弱.能带结构分析发现,O原子的吸附使石墨烯由金属变成半导体,扭转形变发生时,可实现其从半导体到金属、再到半导体特性的转变.扭转角为12°的吸附O原子体系为间接带隙,而其他出现带隙的体系均为直接带隙.与本征石墨烯受扭体系相比,吸附O原子体系的电子结构对扭转形变的敏感度降低,其中扭转角在10°—16°范围内变化时,带隙始终稳定在0.11 eV附近,即在此扭转角范围内始终对应窄带隙半导体.在光学性能中,受扭转形变的吸附体系吸收系数和反射率峰值较未受扭转形变石墨烯吸附O原子体系均减弱,且随着扭转程度的加剧,均出现红移到蓝移的转变.     

N/B掺杂石墨烯的光学与电学性质

石墨烯因其独特的化学成键结构而拥有出色的化学、热学、机械、电学、光学特性.由于石墨烯为零带隙材料,限制了其在纳电子学领域的发展.因此,为了拓宽石墨烯的应用范围,研究打开石墨烯带隙的方法显得尤为重要.本文构建了本征石墨烯、N掺杂石墨烯、B掺杂石墨烯三种模型,研究了本征石墨烯和不同掺杂浓度下的N/B掺杂石墨烯的能带结构、电子态密度及光学与电学性质,包括吸收谱、反射谱、折射率、电导率和介电函数等.研究结果显示:1)本征石墨烯费米能级附近的电子态主要是由C-2p轨道形成,而N/B掺杂石墨烯费米能级附近的电子态主要是由C-2p和N-2p/B-2p轨道杂化形成;2)N/B掺杂可以引起石墨烯费米能级、光学与电学性质的改变,且使狄拉克锥消失,进而打开石墨烯带隙;3)N/B掺杂可以引起石墨烯光学和电学性质的变化,且对吸收谱、反射谱、折射率、介电函数影响较大,而对电导率影响较小.本文的结论可为石墨烯在光电子器件中的应用提供理论依据.     

自由基分子BeH外电场特性

本文采用量子力学从头算方法,运用密度泛函B3LYP方法在6-311G基组水平上对不同外加电场(-0.02—0.02 a.u.)下自由基分子BeH基态的稳定电子结构进行了计算,研究了外电场对BeH分子键长、能量、电荷分布、能级分布、能隙及红外光谱的影响规律.结果表明,随着H→Be方向外电场的增加,分子键长、原子电荷值、偶极矩以及红外强度递减;而能量、能隙和振动频率递增.另外,随着反向电场(Be→H)的增加,能量较大幅度升高.     

外电场对NO在Graphene负载的Pd单原子上的吸附特性的调控

本研究中,通过基于密度泛函理论的第一性原理并考虑范德华力修正计算了Graphene负载的Pd单原子界面特性以及NO的吸附特性(包括吸附构型的结构参数、吸附能和电子结构等),并着重研究了电场对其吸附特性的调控规律及其内在机理.结果表明：1) NO在Pd/Graphene上能够形成较强的化学吸附,吸附能为1.09 eV.吸附的NO分子中的N-O键拉长. Pd-d态与NO-p态的强杂化作用都表明NO分子在Pd-Graphene上被活化. 2)在电场作用下Graphene负载的单原子Pd上的电荷随施加的电场逐渐变化. 3)跟没有施加电场的NO吸附的体系相比,当对NO吸附体系施加沿Z正方向的电场时,NO的吸附增加,吸附的NO从衬底获得更多的负电荷,而Pd所带的正电荷逐步减少;当对NO吸附体系施加沿Z负方向的电场时,NO的吸附减弱,吸附的NO从衬底获得的负电荷逐渐减少,而Pd所带的正电荷逐步增加. 4)外加电场能够有效地调控NO的吸附特性,并调控NO与衬底之间的电荷转移进而调控其电子结构.     

Ti-O共掺杂石墨烯的电子结构和光学性质的理论研究

本文利用基于密度泛函理论的第一性原理方法研究了本征石墨烯和不同掺杂浓度下Ti-O共掺杂石墨烯的电子结构和光学性质,并讨论了其内部的微观机制.研究结果表明:本征石墨烯是一种零带隙材料,狄拉克点在费米能级面上,其在紫外光区的光吸收强度较强.Ti-O共掺杂石墨烯可以很好的打开石墨烯的带隙和提高石墨烯的光催化强度,Ti18-O18@G模型费米能级附近的态密度主要由C-p轨道、Ti-d轨道和O-p轨道杂化而成.Ti18-O18@G模型在可见光区的吸收谱强度最大,主要归因于其内部晶格畸变、带隙被打开和杂质能带的出现,这些因素可以促进电子空穴对的产生和分离,从而使石墨烯在可见光区的光催化能力得到增强.本研究结果可为开发高催化活性的石墨烯提供理论依据.     

Mutual influence of uniaxial tensile strain and point defect pattern on electronic states in graphene

The study deals with electronic properties of uniaxially stressed mono- and multi-layer graphene sheets with various kinds of imperfection: point defects modelled as resonant (neutral) adsorbed atoms or molecules, vacancies, charged impurities, and local distortions. The presence of randomly distributed defects in a strained graphene counteract the band-gap opening and even can suppress the gap occurs when they are absent. However, impurity ordering contributes to the band gap appearance and thereby re-opens the gap being suppressed by random dopants in graphene stretched along zigzag-edge direction. The band gap is found to be non-monotonic with strain in case of mutual action of defect ordering and zigzag deformation. Herewith, the minimal tensile strain required for the band-gap opening (≈12.5%) is smaller than that for defect-free graphene (≈23%), and band gap energy reaches the value predicted for maximal nondestructive strains in the pristine graphene. Effective manipulating the band gap in graphene requires balanced content of ordered dopants: their concentration should be sufficient for a significant sublattice asymmetry effect, but not so much that they may suppress the band gap or transform it into the “quasi- (or pseudo-) gap”.     

Perfect spin filtering controlled by an electric field in a bilayer graphene junction:Effect of layer-dependent exchange energy

Magneto transport of carriers with a spin-dependent gap in a ferromagnetic-gated bilayer of graphene is investigated.We focus on the effect of an energy gap induced by the mismatch of the exchange fields in the top and bottom layers of an AB-stacked graphene bilayer. The interplay of the electric and exchange fields causes the electron to acquire a spindependent energy gap. We find that, only in the case of the anti-parallel configuration, the effect of a magnetic-induced gap will give rise to perfect spin filtering controlled by the electric field. The resolution of the spin filter may be enhanced by varying the bias voltage. Perfect switching of the spin polarization from +100% to -100% by reversing the direction of electric field is predicted. Giant magnetoresistance is predicted to be easily realized when the applied electric field is smaller than the magnetic energy gap. It should be pointed out that the perfect spin filter is due to the layer-dependent exchange energy. This work points to the potential application of bilayer graphene in spintronics.     

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.     

空间电荷效应对热场致发射中诺廷汉效应的影响

热场致发射阴极所产生的强流电子束具有很强的空间电荷效应,为研究该效应对热场致发射过程中诺廷汉（Nottingham）效应的影响机理,在理论分析的基础上,用数值方法研究了不同逸出功和多个外加电场条件下考虑空间电荷效应对诺廷汉效应结果的影响,并与不考虑空间电荷效应时的情形进行了对比. 结果表明：空间电荷效应的强弱会显著影响到阴极表面的稳态电场,进而对诺廷汉效应产生不可忽略的影响;当逸出功在3.0–4.52 eV、外加电场在3×10⁹–9×10⁹ V/m范围内时,考虑空间电荷效应的影响后,热场致发射电子所带走的平均能量较不考虑空间电荷效应时增加0–2.5 eV,且温度越高或外加电场越大时,该增加值越大;考虑空间电荷效应对诺廷汉效应的影响后,热场致发射电子从阴极带走的平均能量随外加电场的增加呈非线性下降规律;当阴极表面温度较高时,诺廷汉效应中的冷却效应随二极管间隙距离的变大而增强. 关键词： 热场致发射 诺廷汉效应 空间电荷效应 阴极表面电场     

电场诱导氧化石墨烯的极化动力学特性研究

本文通过外加电场改变氧化石墨烯团簇分子的共振能量,利用激光激发氧化石墨烯产生的共振荧光特性测量氧化石墨烯在电场作用下的极化动力学特性. 发现存在外加电场使得荧光共振峰的半高全宽趋于饱和的时间特性,而不同的氧化石墨烯团簇分子的荧光共振峰的暂态特性同时反映了电场对氧化石墨烯产生定向极化和变形极化的动力学特性. 关键词： 氧化石墨烯 团簇分子 电场 极化动力学     

A torsional potential for graphene derived from fitting to DFT results

We present a simple torsional potential for graphene to accurately describe its out-of-plane deformations. The parameters of the potential are derived through appropriate fitting with suitable DFT calculations regarding the deformation energy of graphene sheets folded around two different folding axes, along an armchair or along a zig-zag direction. Removing the energetic contribution of bending angles, using a previously introduced angle bending potential, we isolate the purely torsional deformation energy, which is then fitted to simple torsional force fields. The presented out-of-plane torsional potential can accurately fit the deformation energy for relatively large torsional angles up to 0.5 rad. To test our proposed potential, we apply it to the problem of the vertical displacement of a single carbon atom out of the graphene plane and compare the obtained deformation energy with corresponding DFT calculations. The dependence of the deformation energy on the vertical displacement of the pulled carbon atom is indistinguishable in these two cases, for displacements up to about 0.5 Å. The presented potential is applicable to other sp² carbon structures.     

Theoretical investigation of structural and optical properties of semi-fluorinated bilayer graphene

We have studied the structural and optical properties of semi-fluorinated bilayer graphene using density functional theory. When the interlayer distance is 1.62 , the two graphene layers in AA stacking can form strong chemical bonds.Under an in-plane stress of 6.8 GPa, this semi-fluorinated bilayer graphene becomes the energy minimum. Our calculations indicate that the semi-fluorinated bilayer graphene with the AA stacking sequence and rectangular fluorinated configuration is a nonmagnetic semiconductor(direct gap of 3.46 e V). The electronic behavior at the vicinity of the Fermi level is mainly contributed by the p electrons of carbon atoms forming C=C double bonds. We compare the optical properties of the semifluorinated bilayer graphene with those of bilayer graphene stacked in the AA sequence and find that the semi-fluorinated bilayer graphene is anisotropic for the polarization vector on the basal plane of graphene and a red shift occurs in the [010]polarization, which makes the peak at the low-frequency region located within visible light. This investigation is useful to design polarization-dependence optoelectronic devices.     

Electric-field-tunable electronic properties of graphene quantum dots

The tight-binding method is employed to investigate the electronic properties of a square graphene quantum dot subject to an in-plane electric field (F). The electronic properties are strongly modified by tuning the field strength or altering the field direction. F will change state energies, alter energy gaps, and induce energy gap modulations. State energies show oscillatory behavior with the change of the field strength. The oscillating amplitude and period are further modulated by the change of the field direction. The field-orientation-dependent electronic properties originate in the geometrical anisotropy of the square graphene quantum dot. Moreover, the density of states (DOS), exhibiting many discrete peaks, directly reveals the characteristic of the electric-field-tunable electronic properties. The number and frequencies of DOS peaks are significantly dependent on the field strength and direction.     

Tuning the energy gap of bilayer α-graphyne by applying strain and electric field

Our density functional theory calculations show that the energy gap of bilayer α-graphyne can be modulated by a vertically applied electric field and interlayer strain. Like bilayer graphene, the bilayer α-graphyne has electronic properties that are hardly changed under purely mechanical strain, while an external electric field can open the gap up to 120 meV. It is of special interest that compressive strain can further enlarge the field induced gap up to 160 meV, while tensile strain reduces the gap. We attribute the gap variation to the novel interlayer charge redistribution between bilayer α-graphynes.These findings shed light on the modulation of Dirac cone structures and potential applications of graphyne in mechanicalelectric devices.