基于第一性原理的锂空气电池钌掺杂石墨烯正极 氧还原反应机理研究

双电解液锂空气电池因其高理论能量密度受到广泛研究,但电池正极侧氧还原反应(ORR)速率低,其反应速率是限制锂空气电池发展的主要因素之一.本文提出了以钌(Ru)掺杂单层石墨烯作为正极ORR催化剂,采用第一性原理计算nRu (n=1～3)掺杂石墨烯的电子结构和氧气在Ru掺杂石墨烯表面的吸附性能,并以过渡态搜索方法获得ORR反应路径,研究碱性溶液中Ru掺杂单层石墨烯作用下的ORR机理.研究结果表明,经Ru原子掺杂后,石墨烯能够获得稳定的掺杂结构,且电导率显著提升.同原始单层石墨烯相比,Ru掺杂石墨烯增强了对O₂的吸附能力.在三Ru(n=3)掺杂石墨烯表面进行的ORR无需克服任何能垒.此外,三Ru掺杂石墨烯表面对OH基团的吸附能最低,有利于ORR的连续进行.研究表明三Ru掺杂石墨烯有望成为一种新型的ORR催化剂以提高双电解液锂空气电池的性能.     

Anisotropic optical conductivity and electron–hole asymmetry in doped monolayer graphene in the presence of the Rashba coupling

In this study, the optical conductivity of substitutionary doped graphene is investigated in the presence of the Rashba spin orbit coupling (RSOC). Calculations have been performed within the coherent potential approximation (CPA) beyond the Dirac cone approximation. Results of the current study demonstrate that the optical conductivity is increased by increasing the RSOC strength. Meanwhile it was observed that the anisotropy of the band energy results in a considerable anisotropic optical conductivity (AOC) in monolayer graphene. The sign and magnitude of this anisotropic conductivity was shown to be controlled by the external field frequency. It was also shown that the Rashba interaction results in electron–hole asymmetry in monolayer graphene.     

Dynamical thermal conductivity of bilayer graphene in the presence of bias voltage

We study dynamical thermal conductivity of doped biased bilayer graphene for both AA and AB-stacking in the context of tight binding model Hamiltonian. The effects of bias voltage and chemical potential on the behavior of dynamical thermal conductivity are discussed for different stacking of bilayer graphene. Green's function approach has been implemented to find the behavior of thermal conductivity of bilayer graphene within linear response theory. We have found that thermal conductivity decreases with chemical potential for different values of temperature and frequency. Also thermal conductivity of AB stacked bilayer graphene versus bias voltage includes a peak for each value of chemical potential. Furthermore we study the frequency dependence of thermal conductivity of AA stacked bilayer graphene for different values of temperature and bias voltage.     

Bound states of Dirac fermions in monolayer gapped graphene in the presence of local perturbations

In graphene,conductance electrons behave as massless relativistic particles and obey an analogue of the Dirac equation in two dimensions with a chiral nature.For this reason,the bounding of electrons in graphene in the form of geometries of quantum dots is impossible.In gapless graphene,due to its unique electronic band structure,there is a minimal conductivity at Dirac points,that is,in the limit of zero doping.This creates a problem for using such a highly motivated new material in electronic devices.One of the ways to overcome this problem is the creation of a band gap in the graphene band structure,which is made by inversion symmetry breaking(symmetry of sublattices).We investigate the confined states of the massless Dirac fermions in an impured graphene by the short-range perturbations for "local chemical potential" and "local gap".The calculated energy spectrum exhibits quite different features with and without the perturbations.A characteristic equation for bound states(BSs) has been obtained.It is surprisingly found that the relation between the radial functions of sublattices wave functions,i.e.,f_m~+(r),g_m~+(r),and f_m~-(r),g_m~-(r),can be established by SO(2) group.     

Electrical conductivity and resonant states of doped graphene considering next-nearest neighbor interaction

The next-nearest neighbor interaction (NNN) is included in a tight-binding Kubo formula calculation of the electronic spectrum and conductivity of doped graphene. As a result, we observe a wide variation of the behavior of the conductivity, as happens in carbon nanotubes, since the Fermi energy and the resonance peak are not shifted by the same amount when the NNN interaction is included. This finding may have a profound effect on the idea of explaining the minimal conductivity of graphene as a consequence of impurities or defects. Finally, we also estimate the mean free path and relaxation time due to resonant impurity scattering.     

Y掺杂空位石墨烯对NO及CO气体表面吸附的第一性原理研究

摘　要：基于第一性原理的计算方法,建立了本征石墨烯、空位石墨烯及钇( Y)掺杂空位石墨烯模型,并计算了CO、NO在三类石墨烯表面的吸附过程. 从表面能、吸附结构、吸附能和态密度四个方面进行分析讨论,研究掺杂Y对CO、NO气体吸附性能的影响. 结果表明：CO、NO与本征石墨烯之间的吸附为弱的物理吸附,掺杂Y后增强了材料表面对CO、NO的吸附效果,最大吸附能分别为7.414eV、6.702eV,属于化学吸附;掺杂Y使空位石墨烯费米能级附近有了更多的活跃电子,其吸附NO后体系由半金属转变为金属特性,该特性能为开发更加优良的石墨烯气敏材料提供理论支持.     

空位缺陷对金属基外延石墨烯态密度和电导率的影响

考虑到空位缺陷的存在和原子非简谐振动,以铜、镍基外延石墨烯为例, 研究了金属基外延石墨烯空位缺陷浓度和态密度以及电导率随温度的变化规律,探讨了空位缺陷的影响。结果表明：(1) 空位缺陷浓度随温度升高而非线性增大,外延石墨烯的空位缺陷浓度及其随温度的变化率均大于石墨烯; (2) 与石墨烯相同,金属基外延石墨烯的态密度变化曲线对电子能量为0为对称,但空位缺陷的存在使态密度在电子能量为零时的值不为零,空位缺陷对导带态密度的影响大于价带;态密度随空位缺陷浓度的增大而线性减小,但减小幅度不大,而温度对石墨烯态密度几乎无影响;（3）金属基外延石墨烯的电导率近似等于电子声子相互作用贡献的电导率,并随温度升高而非线性减小;空位缺陷的存在使电导率有所减小,但只在较高温度下才明显。原子非简谐振动情况的电导率稍大于简谐近似的电导率,温度愈高,两者电导率的差愈大,即非简谐效应愈显著。     

Fe,Co,Ni掺杂石墨烯表面吸附C_2H_4的第一性原理研究

基于密度泛函理论(DFT)的广义梯度近似(GGA),本文对本征石墨烯以及掺杂Fe,Co,Ni石墨烯的几何结构和电子性质进行了优化计算,并计算了C_2H_4在本征石墨烯以及掺杂石墨烯表面的吸附过程,讨论了体系的吸附能、稳定性、DOS及掺杂对键长的影响.结果表明C_2H_4在本征石墨烯B位的吸附和掺杂石墨烯的吸附为化学吸附,在本征石墨烯T和H位的吸附为物理吸附;掺杂后石墨烯的比表面积增大,与本征石墨烯相比,掺杂使费米能级附近的态密度积分显著提高,表明掺杂石墨烯的电导性会发生变化,从而影响对C_2H_4的气敏度..C_2H_4在Fe、Co、Ni分别掺石墨烯的最佳吸附位为T位、H位和B位;掺杂Fe,Ni后体系的吸附能力显著提高,且掺杂Ni时体系的吸附能力最好.     

Electron transport in Ti1−xNbxO2 solid solutions with x < 4%

By means of conductivity and thermopower measurements in niobium doped rutile TiO₂, we have analysed the electron transport. A previous study made in TiO₂ pointed out the existence of a large polaron transport. Nevertheless, some uncertainties remain as the precise dependence of the mobility with the temperature. The Nb doped TiU₂ studied in the present paper brings some new information: the mobility could follow an optical phonon scattering law. The FHIP model seems to be the more appropriate model to describe the mobility but the lack of theoretical calculation of transport energy does not allow definitive conclusions about the physical processes which occur in the intermediate range of temperature. However, we can say that the ionization activation energy of Nb is found to be close to 14 eV.Moreover, it is found that the localized electrons become mobile by hopping with increasing niobium content. This yields a conductivity composed by electrons which move in the 3d Ti band and localized electrons which hop from site to site. This hopping component and the number of localized electrons increase with niobium content. This leads to the disappearance of the band motion in the conductivity.     

双空位掺杂氟化石墨烯的电子性质和磁性

基于密度泛函理论,计算了外来原子X(Al,P,Ga,As,Si)双空位替代掺杂氟化石墨烯的电子特性和磁性.通过对计算结果分析发现,与石墨烯的双空位掺杂类似,氟化石墨烯的双空位掺杂也是一种较为理想的掺杂方式.通过不同原子掺杂,氟化石墨烯的电子性质与磁性均发生很大变化:Al和Ga掺杂使氟化石墨烯由半导体变为金属,并且具有磁性;P和A8掺杂使氟化石墨烯变为自旋半导体;Si掺杂氟化石墨烯仍是半导体,只改变带隙且没有磁性.进一步讨论磁性产生机制获得了掺杂原子浓度与磁性的关系,并且发现不同掺杂情况的磁性是由不同原子的不同轨道电子引起的.双空位掺杂不仅丰富了氟化石墨烯的掺杂方式,其不同电磁特性也使此类掺杂结构在未来的电子器件中具有潜在应用.     

Effect of vanadium doping on the electrical properties of Bi12GeO20 crystals

A study is reported of the temperature dependences of the dc and ac electrical conductivities, as well as of I–V characteristics of pure and vanadium-doped germanosillenite crystals. It has been established that the charge carriers in Bi₁₂GeO₂₀ are electrons and holes. Doping with vanadium gives rise to a strong dependence of the conductivity and its activation energy on the dopant concentration. Within the model, the results explain the hopping-charge transfer in doped, closely compensated semiconductors.     

利用尿素热退火方法制备氮掺杂石墨

在尿素气氛中,通过热退火实验实现石墨烯的氮掺杂. 结合光电子能谱和拉曼光谱,确定了氮在石墨烯中的掺杂构型,并发现掺杂量可以通过退火温度和时间加以调控. 电性测量表明掺杂石墨烯的电导同氮掺杂量有很好的关联性.     

Coulomb interactions of massless Dirac fermions in graphene; pair-distribution functions and exchange-driven spin-polarized phases

The quasi-2D electrons in graphene behave as massless fermions obeying a Dirac-Weyl equation in the low-energy regime near the two Fermi points. The stability of spin-polarized phases (SPP) in graphene is considered. The exchange energy is evaluated from the analytic pair-distribution functions, and the correlation energies are estimated via a closely similar four-component 2D electron fluid which has been investigated previously. SPPs appear for sufficiently high doping, when the exchange energy alone is considered. However, the inclusion of correlations is found to suppress the spin-phase transition in ideal graphene.     

基于密度泛函理论研究掺杂Pd石墨烯吸附O2及CO

基于第一性原理的密度泛函理论研究了单个O₂和CO气体分子吸附于本征石墨烯和掺杂钯(Pd)的石墨烯的体系, 通过石墨烯掺Pd前后气体分子的吸附能、电荷转移及能带和态密度的计算, 发现掺Pd后气体分子吸附能和电荷转移显著增大, 这是由于Pd的掺杂, 在本征石墨烯能带中引入了杂质能级, 增强了石墨烯和吸附气体分子间的相互作用; 氧化性气体O₂和还原性气体CO吸附对石墨烯体系能带结构和态密度的影响明显不同, 本征石墨烯吸附O₂后, 费米能级附近态密度变大, 掺Pd后在一定程度变小; 吸附还原性的CO后, 石墨烯费米能级附近态密度几乎没有改变, 表明掺杂Pd不会影响石墨烯对CO的气体灵敏度, 但由于CO对石墨烯的吸附能增大, 可以提高石墨烯对还原性气体的气敏响应速度.     

Br掺杂对石墨烯带隙影响的实验研究

石墨烯独特的结构和性能使其在纳米电子、半导体器件等领域成为研究的热点,但其零带隙的特性严重限制了其应用.采用化学气化沉积法制备了多层石墨烯,并使用溴蒸汽对制备的多层石墨烯进行掺杂,分析研究了溴蒸汽化学掺杂对石墨烯带隙的影响.为了对比溴蒸汽掺杂对石墨烯带隙的影响,使用633 nm He-Ne光分别测量了石墨烯掺杂前和掺杂后的拉曼光谱,根据拉曼光谱计算了石墨烯费米能级移动与掺杂溴蒸汽之间的关系.实验结果表明:溴蒸汽掺杂对石墨烯拉曼光谱G带产生影响;随着掺杂溴蒸汽体积的增加,拉曼光谱G带向高频移动并逐渐趋于稳定;G带和2D带强度比也迅速增加,并最终趋于稳定.费米能级的移动与G峰位置成线性关系,利用G峰峰值位置与费米能级实验关系式计算了溴掺杂后石墨烯的费米能级,分析了化学掺杂对石墨烯带隙的影响.     

The influence of the band structure of epitaxial graphene on SiC on the transistor characteristics

We fabricated high-mobility field-effect transistors based on epitaxial graphene synthesized by vacuum graphitization of both the Si- and C-faces of SiC. Room-temperature field-effect mobilities >4000 cm²/V s for both electrons and holes were achieved, although with wide distributions. By using a high-k gate dielectric, we were able to measure the transistor characteristics in a wide carrier density range, where the mobility is seen to decrease as the carrier density increases. We formulate a simple semiclassical model of electrical transport in graphene, and explain the sublinear dependence of conductivity on carrier density from the view point of the few-layer graphene energy band structure. Our analysis reveals important differences between the few-layer graphene energy dispersions on the SiC Si- and C-faces, providing the first evidence based on electrical device characteristics for the theoretically proposed energy dispersion difference between graphene synthesized on these two faces of SiC.     

B、N掺杂对钠在石墨烯上吸附性能的影响

采用基于密度泛函理论的第一性原理方法,研究了本征石墨烯及缺陷石墨烯对Na原子的吸附行为。主要研究了三种石墨烯：本征石墨烯、B掺杂的石墨烯和N掺杂的石墨烯。结果表明,与本征石墨烯相比,B掺杂的石墨烯和N掺杂的石墨烯在吸附能、电荷密度、态密度和储钠量方面表现出很大的差异。B掺杂的石墨烯对Na原子的吸附能是-1.93 eV,约为本征石墨烯对Na原子吸附能的2.7倍;与本征石墨烯相比,N掺杂的石墨烯对Na原子的吸附能明显增大。态密度计算结果表明,Na原子与B掺杂的石墨烯中的B原子发生轨道杂化,而本征石墨烯和N掺杂的石墨烯中不存在轨道杂化现象。B掺杂的石墨烯对Na原子的吸附量是3个,与本征石墨烯相比显著提高。因此,B掺杂的石墨烯有望成为一种新型的储钠材料。     

B、N掺杂对钠在石墨烯上吸附性能的影响

采用基于密度泛函理论的第一性原理方法,研究了本征石墨烯及缺陷石墨烯对Na原子的吸附行为.主要研究了三种石墨烯:本征石墨烯、B掺杂的石墨烯和N掺杂的石墨烯.结果表明,与本征石墨烯相比,B掺杂的石墨烯和N掺杂的石墨烯在吸附能、电荷密度、态密度和储钠量方面表现出很大的差异.B掺杂的石墨烯对Na原子的吸附能是-1.93 e V,约为本征石墨烯对Na原子吸附能的2.7倍;与本征石墨烯相比,N掺杂的石墨烯对Na原子的吸附能明显增大.态密度计算结果表明,Na原子与B掺杂的石墨烯中的B原子发生轨道杂化,而本征石墨烯和N掺杂的石墨烯中不存在轨道杂化现象.B掺杂的石墨烯对Na原子的吸附量是3个,与本征石墨烯相比显著提高.因此,B掺杂的石墨烯有望成为一种新型的储钠材料.     

Magnetoplasma excitations and the effect of electron and hole velocity renormalization in free-hanging graphene studied by Raman scattering

The properties of plasma and magnetoplasma excitations in free-hanging graphene have been studied for the first time by Raman scattering. In addition to single-particle excitations associated with transitions between empty Landau levels of electrons and holes, collective plasma and magnetoplasma excitations in the system of electrons (and holes) of various densities have been discovered for the first time. Hybridization of plasma and cyclotron modes corresponding to the Kohn law has been shown to occur in the limit of high filling factors, which allows measuring directly the plasma and cyclotron energies. The dependence of the electron and hole velocities on their density has been investigated via the magnetic-field dependence of the cyclotron energy in free-hanging graphene. The effect of strong renormalization of the electron and hole dispersion relations seen as an increase in the velocity (by 40–50%) with a decrease in the charge-carrier density to 10¹¹ cm^–2 has been discovered. The charge-carrier density dependences of the widths of magnetoplasma resonances in free-hanging graphene and graphene lying on a silicon dioxide surface have been measured and shown to be at least 3.5 and 14.8 meV, respectively.     

The effect of Holstein phonons on the electrical conductivity of doped monolayer graphene

Electrical conductivity of graphene sheets is studied in the presence of coupling between lattice optical vibrations and electrons. Green's function approach is implemented to find the temperature behavior of electrical conductivity. Moreover, the effect of electronic doping on the electrical conductivity of graphene with electron–phonon interaction is investigated. Our results show that electrical conductivity increases as a function of temperature at low temperature and gets a maximum value and then decays at high temperature.