非晶碳结构建模和电子结构的第一性原理研究

基于密度泛函理论,采用了一种更为精确的交换相关泛函OLYP(OPTX+LYP),对密度范围从2.0到3.2 g/cm³的非晶碳进行结构建模. 模拟得到的5个碳网络结构无论从径向分布函数还是sp³含量都与实验符合得很好. 对非晶碳电子结构的研究表明费米能级附近的电子态密度主要是sp²碳原子的贡献. 随着密度的增加,sp³碳原子增加,费米能级附近的态密度越来越小. 小环结构增加了费米能级附近的电子态密度,缺陷态在费米能级形 关键词： 非晶碳 密度泛函理论 电子结构     

掺氮四面体非晶碳的第一性原理研究

采用基于第一性原理的分子动力学方法对掺氮四面体非晶碳进行结构建模,并对其显微结构和电子结构进行了研究. 氮在非晶碳网络中的配位形态与密度没有明显关系,主要是以三配位形态存在,其次是两配位,四配位氮的比例很小. 掺氮后碳网络结构sp²含量大大增加,随着氮含量的增加,费米能级附近态密度增加. 氮掺入后并未使费米能级发生明显移动. 关键词： 掺氮四面体非晶碳 第一性原理 密度泛函理论 电子结构     

氮离子轰击能量对ta-C:N薄膜结构的影响

利用磁过滤真空阴极电弧技术制备了sp³键含量不小于80%的四面体非晶碳薄膜(ta-C), 然后通过氮离子束改性技术制备了氮掺杂的四面体非晶碳(ta-C:N)薄膜. 利用Raman光谱和X射线光电子能谱对薄膜结构的分析,研究了氮离子轰击能量对ta-C:N薄膜结构的影响. 氮离子对ta-C薄膜的轰击,形成了氮掺杂的ta-C:N薄膜. 氮离子轰击诱导了薄膜中sp³键向sp²键转化, 以及CN键的形成.在ta-C:N薄膜中,氮掺杂的深度和浓度随着氮离子能量的增大而增大. ta-C:N薄膜中sp²键的含量和sp²键团簇的尺寸随着氮离子轰击能量的增大而增加; 在ta-C:N薄膜中, CN键主要由C-N键和C＝N键构成, C-N 键的含量随着氮离子轰击能量的增大而减小,但是C＝N 键含量随着氮离子轰击能量的增大而增大.在ta-C:N薄膜中不含有C≡N键结构.     

用SCLC法研究低k多孔SiO2:F薄膜的隙态密度

用溶胶-凝胶法制备了低k多孔SiO₂:F薄膜，用空间电荷限制电流法(SCLC)研究了多孔SiO₂:F薄膜中的隙态密度以及掺F量对隙态密度的影响，得到了平衡费米能级附近的隙态密度约为7×10¹⁵cm^-3·eV^-1，以及带隙中隙态随能量的分布. 并对造成隙态的主要原因也进行了讨论.     

Ti掺杂NbSe2电子结构的第一性原理研究

采用基于密度泛函理论框架下的第一性原理平面波超软赝势方法, 计算了理想2H-NbSe₂和Ti掺杂2H-NbSe₂晶体的几何结构及电子结构; 对掺杂前后超胞的能带图、态密度及分波态密度图进行了分析. 结果表明, 掺杂后费米能级附近能量区域的电子态密度出现了较高的峰值, 且费米能级位置发生了改变. 理论上可以认为Ti的掺杂会使得NbSe₂的导电性增强, 有利于开发新型的电接触复合材料.     

掺溴非晶碳梯度薄膜的制备与分析

 采用低压等离子增强化学气相沉积法用溴乙烷、氢气制备了掺溴的非晶碳梯度薄膜。通过样品的XPS能谱分析研究了薄膜沉积速率与氢气流量、溴元素原子分数与溴乙烷流量以及溴元素原子分数与刻蚀时间之间的关系，得出了溴乙烷流量、刻蚀时间对薄膜的主要键态含量、C元素sp²/sp³键态杂化比和薄膜硬度的影响。结果表明：薄膜沉积速率随氢气流量的增加而线性减小，溴元素含量随溴乙烷流量的增加先增加后降低，刻蚀时间越长，溴乙烷流量越小，薄膜越硬     

BC5力学性质的第一性原理计算

采用平面波赝势密度泛函理论方法对0—60 GPa静水压下BC₅ 六角晶系P3m1和四方晶系I4m2结构的平衡态晶格常数、弹性常数、各向异性以及泊松比与Cauchy扰动进行了研究. 研究结果表明, BC₅的两种结构在高压下是稳定的, 且不可压缩性随着压强的增加而增大. 另外, 对其电子结构也进行了计算, 计算结果表明, BC₅存在一个较宽的带隙, 两种原子间有较强的共价杂化, 材料的性质主要由B的2p¹和C的2p²态电子共同决定. 压强对材料带隙和费米能级附近的态密度几乎没有影响, 只引起微小的漂移, 可推断其很好的高压稳定性.     

贵金属（Cu、Ag、Au）掺杂ZnO电子结构和光学性质的第一性原理研究

采用基于密度泛函理论的总体能量平面波超软赝势方法,对贵金属（Cu、Ag、Au）掺杂ZnO进行了几何结构优化,并计算了相应的能带结构、受主能级、形成能、电子态密度和光学性质. 结果表明：贵金属掺杂后带隙增加且体系费米能级附近电子态密度主要来源于Cu3d、Ag4d和Au5d态电子的贡献. 与未掺杂ZnO相比,介电函数虚部、反射峰强度和吸收系数在可见光和紫外区域增强. 能量损失谱计算表明,贵金属（Cu、Ag、Au）掺杂后ZnO的等离子体共振频率峰发生蓝移.     

Al和N共掺p型Zn1-xMgxO电子结构的第一性原理计算

采用密度泛函理论下的第一性原理平面波超软赝势方法,对Zn1-xMgxO超晶胞和掺杂Al,N后的Zn1-xMgxO超晶胞分别进行了优化计算.结合广义梯度近似计算了Al和N共掺杂后Zn1-xMgxO的能带结构、电子态密度和Mulliken电荷布居分布.计算表明:掺入N原子的2p态电子为Zn1-xMgxO价带顶提供空穴载流子,使Zn1-xMgxO价带顶向高能方向移动;掺入Al原子的3p态电子则与N原子的2p态电子在费米能级附近发生轨道杂化,使费米能级处价带能级展宽,Al和N共掺杂可获得p型Zn1-xMgxO.     

Mn、Fe掺杂ZnS的第一性原理计算

采用基于密度泛函理论(DFT)的第一性原理平面波超软赝势方法,计算了闪锌矿结构的纯净ZnS、Mn掺杂ZnS和Fe掺杂ZnS的电子结构和光学性质,分析了掺杂对ZnS晶体的能带结构、电子态密度、光学吸收系数的影响。计算结果表明:掺杂体系费米能级附近的电子态密度主要来源于Mn 3d,Fe 3d态电子的贡献;Mn、Fe掺杂情况下的光吸收谱均向低能级方向移动且在低能端形成新的吸收峰,红移效应明显。     

Direct fabrication and IV characterization of sub-surface conductive channels in diamond with MeV ion implantation

In the present work we report about the investigation of the conduction mechanism of sp² carbon micro-channels in single crystal diamond. The structures are fabricated with a technique which employs a MeV focused ion-beam to damage diamond in conjunction with variable thickness masks. This process changes significantly the structural properties of the target material, because the ion nuclear energy loss induces carbon conversion from sp³ to sp² state mainly at the end of range of the ions (few micrometers). Furthermore, placing a mask with increasing thickness on the sample it is possible to modulate the channels depth at their endpoints, allowing their electrical connection with the surface. A single-crystal HPHT diamond sample was implanted with 1.8 MeV He⁺ ions at room temperature, the implantation fluence was set in the range 2.1×10¹⁶-6.3×10¹⁷ ions cm^-2, determining the formation of micro-channels with a graded level of damage extending down to a depth of about 3 μm. After deposition of metallic contacts at the channels’ endpoints, the electrical characterization was performed measuring the I-V curves at variable temperatures in the 80-690 K range. The Variable Range Hopping model was used to fit the experimental data in the ohmic regime, allowing the estimation of characteristic parameters such as the density of localized states at the Fermi level. A value of 5.5×10¹⁷ states cm^-3 eV^-1 was obtained, in satisfactory agreement with values previously reported in literature. The power-law dependence between current and voltage is consistent with the space charge limited mechanism at moderate electric fields.     

Photostimulation of conductivity and electronic properties of field-emission nanocarbon coatings on silicon

The electronic structure of island carbon films on silicon, which are capable of low-voltage field electron emission (at the mean electric-field strength above several hundreds of V/mm), have been investigated. It has been shown by tunnel spectroscopy that islands of these coatings are characterized by a continuous spectrum of the allowed delocalized states near the Fermi level, i.e., they contain carbon in the sp ² state. The photoconductivity of the coatings under study has been observed. Based on the current and spectral characteristics of this phenomenon, it has been shown that islands are separated from each other by tunnel barriers and from the substrate by a Schottky barrier.     

Correlations between the physical properties of the carbon phases obtained at a high pressure from C<Subscript>60</Subscript> fullerite

Correlations between the density, elastic properties, and hardness of the carbon phases prepared from C₆₀ at a high pressure are studied. By varying the high pressure and temperature properly, one can obtain from C₆₀ a broad class of ordered polymerized and disordered phases, for which the fraction of the sp² and sp³ states, the characteristic dimensionality of the structure, the degree of covalent bonding, etc. can be varied successfully. 3D-bonded carbon structures are shown to exhibit a clearly pronounced correlation between the hardness or bulk modulus and the density, with these correlations also apparently applying to the carbon phases in a general case. At the same time, the mechanical characteristics of structures with a lower dimension covalent bonding are worse than those of 3D-bonded phases with similar values of the density.     

Electronic and transport properties of monolayer graphene defected by one and two carbon ad-dimers

Using density functional theory combined with non-equilibrium Green’s function method, we have investigated the electronic and transport properties of graphenes defected by one and two carbon ad-dimers (CADs), placed parallel to the graphene lattice. Addition of these CADs to graphenes creates 3D paired pentagon–heptagon defects (3D-PPHDs). The band structure, density of states (DOS), quantum conductance, projected DOS, as well as the current–voltage characteristic per graphene super-cells containing each type of 3D-PPHD are calculated. The local strain introduced to graphene by 3D-PPHDs forces the C-bonds in the dimers to hybridize in sp ³-like rather than sp ²-like orbitals, creating localized states at the center of the corresponding defect below the Fermi energy. Simulations show that the zero-bias conductances per super-cells containing defects created by one and two CADs exhibit dip about ~0.579 and ~0.253 eV below their corresponding Fermi levels, respectively. These can be attributed to the localized states around the same energy levels. Simulations also show that the enhanced carriers scatterings within the graphenes defected by the 3D-PPHDs have increased their overall resistances, as compared with the pristine graphene. Moreover, the current–voltage characteristic calculated per super-cell for each case shows that the current for those containing one and two CADs, at an applied voltage of 0.5 V, is ~5 and 13 % less than the current calculated for the pristine super-cell of the same size.     

Electronic properties of Semi-Insulating Polycrystalline-Silicon (SIPOS) doped with oxygen atoms

The temperature dependence of the electrical conductivity of SIPOS shows that there are two kinds of conduction mechanisms, conduction in extended states and hopping conduction through localized states dominant above and below room temperature, respectively. The change in the conductance of a SIPOS film due to a transverse electric field can well be understood by the CFO model of amorphous semiconductors and indicates that the Fermi level in the thermal equilibrium is near the midgap, and the results show the density of localized states at the Fermi level to be about 10²⁰ cm^?3 eV^?1.     

Cr adsorption induced magnetism in Bi2Se3 film by proximity effects

Based on first-principles calculations within density functional theory, we studied the effects of Cr adsorption on the electronic and magnetic properties of Bi₂Se₃ topological insulators employing spin–orbit coupling (SOC) self-consistently. Cr atom induces a spin-polarization with total net magnetic moments of 2.157 μ_B (spin up). There is a p-d hybridization between the Cr 3d states and the nearest neighbor Se 4p states. A peak of density of states appears at Fermi level. The electronic structures change and the energy levels split near the Fermi level. No gap opening has been found at the Dirac point of the surface state from the bottom surface.     

Investigation of microstructure and?photo-magnetic properties of?sulfur-doped DLC nanocomposite films by?electrochemical method

Sulfur-doped DLC nanocomposite films have been successfully deposited by the electrochemical method using the mixture of methanol and thiofuran as the precursor at ambient atmospheric pressure. In contrast to DLC film, the effects of sulfur incorporation on the microstructural transformation and properties of sulfur-doped DLC nanocomposite films were investigated in detail in terms of atomic force microscopy, X-ray photoelectron spectroscopy, Raman spectrum and photoluminescence and magnetic tests. The experimental results showed that the unexpected organic molecular structure was formed like sulfone or thiols in sulfur-doped DLC nanocomposite films, and the concentration of sulfur in films was readily manipulated by the volume ratio of thiofuran to methanol. Meanwhile, the sp³-hybridized carbon content gradually decreased in films as the volume of thiofuran increased. Furthermore, sulfur-doped DLC nanocomposite films showed the monochromatic photoluminescence performance with a wide band centered at 510 nm, which could be attributed to carrier localization within an increasing sp² clusters and the defects along with the sulfur doping. Particularly, ferro-like magnetic performance of sulfur-doped DLC nanocomposite film might originate from the magnetic moment of localized sp² clusters with different charged carriers near the Fermi level after sulfur incorporation.     

Role of 3D-paired pentagon–heptagon defects in electronic and transport properties of zigzag graphene nanoribbons

Electronic and transport properties of 11 zigzag graphene nanoribbons (11-z-GNRs) with two types of 3D-paired pentagon–heptagon defects (3D-PPHDs) are studied using density functional theory combined with non-equilibrium Green’s function method. The C ad-dimers that have been introduced to z-GNRs to form these 3D-PPHDs have induced local strains forcing the C-bonds in the ad-dimers to hybridize in sp³-like rather than sp²-like orbitals. Such transformations that cause extra electrons to accumulate around the 3D-PPHDs are responsible for the variations in the electronic and transport properties of the defected z-GNRs. Density of states (DOS) for 11-z-GNRs containing either type of 3D-PPHDs, compared with that of the pristine 11-z-GNR, exhibits a peak at a particular energy level below the Fermi level, within its first plateau. Each peak, corresponding to a dip in the related zero-bias conductance profile, is attributed to electrons trapped in the localized states around the same energy level. The current–voltage (I–V) characteristics are almost linear for 11-z-GNR defected by either type of 3D-PPHD. Presence of a 3D-PPHD, made by addition of a single C ad-dimer, above an 11-z-GNR super-cell decreases its average conductance by 10.7 %, while a 3D-PPHD made by addition of two C ad-dimers to the opposite sides of the same 11-z-GNR super-cell decreases its conductance by 23 %.