Surface energy and hybridization studies of amorphous carbon surfaces

Surface properties of a large number of amorphous carbon (a-C) films have been investigated using contact angle measurements and X-ray photoelectron spectroscopy (XPS). Dense a-C surfaces with variable sp³/(sp² + sp³) average hybridization were grown using sputtering or pulsed laser deposition (PLD) and were further chemically modified by thermal annealing, ion bombardment or covalent grafting of organic monolayers. The average carbon hybridization, impurity level and mass density, were deduced from XPS and photoelectron energy loss spectroscopy (PEELS). The depth sensitivity of the dispersive (Lifshitz–van der Waals) interaction, estimated at 1–2 nm from the dependence of γ^LW on the grafted perflorodecene molecule coverage, is much better than XPS which probes a 3–5 nm depth. The observation of a non-monotonic behavior in the correlation between surface hybridization and electron donor component of surface energy reveals that the average carbon hybridization alone does not describe the entire surface energy physics. The role of π bond clustering in the polar interactions is thus considered and some implications on surface reactivity and mutual interactions with molecular or biomolecular species are discussed.     

Deposition and characterization of carbon nitride films from hexamethylenetetramine/N2 by microwave plasma-enhanced chemical vapor deposition

Carbon nitride thin films were deposited on Si(1 0 0) substrate by microwave plasma-enhanced chemical vapor deposition (PECVD). Hexamethylenetetramine (HMTA) was used as carbon and nitrogen source while N₂ gas was used as both nitrogen source and carrier gas. The sp³-bonded C---N structure in HMTA was considered significantly in the precursor selection. X-ray diffraction analysis indicated that the film was a mixture of crystalline - and β-C₃N₄ as well as graphitic-C₃N₄ and β-Si₃N₄ which were not easily distinguished. Raman spectroscopy also suggested the existence of - and β-C₃N₄ in the films. X-ray photoelectron spectroscopy study indicated the presence of sp²- and sp³-bonded C---N structures in the films while sp³C---N bonding structure predominated to the sp² C---N bonding structure in the bulk composition of the films. N was also found to be bound to Si atoms in the films. The product was, therefore, described as CN_x:Si, where x depends on the film depth, with some evidences of crystalline C₃N₄ formation.     

Field emission properties and surface structure of nickel containing amorphous carbon

Nickel containing amorphous carbon (a-C:Ni) films have been deposited by filtered cathodic vacuum arc (FCVA) technique by introducing pure nickel into the graphite target. The field electron emission property of a-C:Ni was improved when compared to that of pure tetrahedral amorphous carbon (ta-C) by FCVA. The emission threshold field of a-C:Ni film is about 5 V μm⁻¹, whilst the threshold field of the ta-C film is about 13 V μm⁻¹. Raman spectroscopy suggests that the sp² clusters in the carbon film increase both in size and number when Ni is introduced. However, the emission was found to degrade to threshold fields beyond 20 V μm⁻¹ after the a-C:Ni film was left in ambient for a week. This observation is attributed to surface absorption of oxygen on the a-C:Ni film, as determined by X-ray Photoelectron Spectroscopy.     

Effects of post-annealing on crystalline and transport properties of Bi_2Te_3 thin films

A well-established method is highly desirable for growing topological insulator thin films with low carrier density on a wafer-level scale. Here, we present a simple, scalable method based on magnetron sputtering to obtain high-quality Bi_2 Te_3 films with the carrier density down to 4.0 × 10~(13) cm~(-2). In contrast to the most-used method of high substrate temperature growth, we firstly sputtered Bi_2 Te_3 thin films at room temperature and then applied post-annealing. It enables the growth of highly-oriented Bi_2 Te_3 thin films with larger grain size and smoother interface. The results of electrical transport show that it has a lower carrier density as well as a larger coherent length(～ 228 nm, 2 K). Our studies pave the way toward large-scale, cost-effective production of Bi_2 Te_3 thin films to be integrated with other materials in wafer-level scale for electronic and spintronic applications.     

Microstructural analysis of hard amorphous carbon films deposited with high-energy ion beams

Hard amorphous carbon films produced using high-energy (ca. 30 keV) ion beam deposition of CH₃⁺ and CH₄⁺ on silicon wafers, have been investigated by Positron Annihilation Spectroscopy (PAS), the results are correlated with Raman Spectroscopy and Electrical Resistivity measurements. The microstructural modifications of the films as a function of the annealing temperature in the 300–600°C range have been studied. The evolution of the fractions of sp² and sp³ bonds is described and related to the changes of the open volume defect distribution and the graphitization process.     

富勒烯C20四聚体的结构与性能研究

采用密度泛函理论(DFT)中的杂化密度泛函(B3LYP)方法, 在6-31 G基组水平上对C₂₀四聚体进行了几何参数全优化, 得到了基态构型, 并对其稳定性、电子结构、极化率和芳香性进行了计算研究. 结果表明: C₂₀碳笼以[2+2]加成方式结合形成C₂₀四聚体, 具有良好的热力学稳定性; C原子内部以sp²的方式杂化, C原子之间有少量电荷转移; C₂₀ 四聚体的IR和Raman光谱都有较多的振动峰; 随碳笼数的增加, C₂₀聚合物中原子间的成键相互作用随之增强; C₂₀四聚体具有芳香性.     

Electronic Properties of Fullerenes for Two Kinds of Hybridized Orbits

The electronic hopping energies and the band structure of a neutral C₆₀ molecule for two kinds of hybridized orbits, sp³ and sp², are studied using the Wannier function method and tight-binding approximation model, respectively. By comparison, the sp³ hybridized type is superior in the band structure obtained by employing the Wannier function method. When the effective nuclear charge number Z = 1.148 the energy gap (t_lu-h_u), bandwidth (t_3g-a_g) and threshold value (t_3g-h_u) of the ionization energy are 1.70 eV, 11.35 eV and 7.69 eV, respectively. These results are in accord with the experimental values.     

MgO(111)衬底MgB2 超薄膜的制备和性质研究

利用混合物理化学气相沉积法(HPCVD)在MgO(111)衬底上制备了干净的MgB₂超导超薄膜. 在背景气体压强, 载气氢气流量以及沉积时间一定的情况下, 改变B₂H₆的流量, 制备得到不同厚度系列的MgB₂超导薄膜样品, 并测量了其超导转变温度 T_c, 临界电流密度J_c等临界参量. 该系列超导薄膜沿c轴外延生长, 表面具有良好的连接性, 且有很高的超导转变温度T_c(0) ≈ 35-38 K和很小的剩余电阻率ρ(42 K) ≈ 1.8-20.3 μΩ·cm^-1. 随着膜厚的减小而减小, 临界温度变低, 而剩余电阻率变大. 其中20 nm的样品在零磁场, 5K时的临界电流密度J_c ≈ 2.3×10⁷ A/cm². 表明了利用HPCVD在MgO(111)衬底上制备的MgB₂超薄膜有很好的性能, 预示了其在超导电子器件中广阔的应用前景. 关键词： MgO(111)衬底 2超薄膜')" href="#">MgB₂超薄膜 混合物理化学气相沉积     

C+注入a-SiNx：H薄膜的微结构及光发射的研究

常温下对低压化学气相沉积制备的纳米硅镶嵌结构的a-SiN_x:H薄膜进行低能量高剂量的C⁺注入后,在800~1200℃高温进行常规退火处理。X射线光电子能谱(XPS)及X射线光电子衍射(XRD)等实验结果表明,当退火温度由800℃升高到1200℃后,薄膜部分结构由SiC_xN_y转变成SiN_x和SiC的混合结构。低温下利用真空紫外光激发,获得分别来自于SiN_x、SiC_xN_y、SiC的,位于2.95,2.58,2.29 eV的光致发光光谱。随着退火温度的升高,薄膜的结构发生了变化,发光光谱也有相应的改变。     

β石墨炔衍生物结构稳定性及电子结构的密度泛函理论研究

石墨炔衍生物比石墨烯具有更多样化的原子结构,因而具有潜在的更丰富的电子结构.通过第一性原理密度泛函理论研究方法系统研究了β石墨炔衍生物的结构稳定性、原子构型和电子结构.本文计算的β石墨炔衍生物系列体系由六边形碳环(各边原子数N=1—10)通过顶点相连而成.对结构与能量的计算分析表明:当N为偶数时,β石墨炔拥有单、三键交替的C—C键结构,其能量比N为奇数时,拥有连续C=C双键的石墨炔衍生物更稳定.计算的能带结构和态密度显示:根据碳环各边原子个数N的奇偶性不同,β石墨炔可呈现金属性(N为奇数时)或半导体特性(N为偶数时).该奇偶依赖的原子构型和电学性质是由Jahn-Teller畸变效应导致,与碳环各边原子碳链的实际长度无关.计算发现部分半导体β石墨炔(N=2,6,10)呈现狄拉克锥能带特征,其带隙约10 meV,且具有0.255×10~6—0.414×10~6m/s的高电子速度,约为石墨烯电子速度的30%—50%.本密度泛函理论研究表明,将sp杂化碳原子引入石墨烯六边形碳环的边上,可通过控制六边形各边原子个数的奇偶性调制其金属和半导体电子特性或狄拉克锥的形成,为免掺杂和缺陷调控纳米碳材料的电学性质和设计碳基纳米电子器件提供了理论依据.     

Effect of Cu doping on the secondary electron yield of carbon films on Ag-plated aluminum alloy

Reducing the secondary electron yield (SEY) of Ag-plated aluminum alloy is important for high-power microwave components. In this work, Cu doped carbon films are prepared and the secondary electron emission characteristics are studied systematically. The secondary electron coefficient δ_max of carbon films increases with the Cu contents increasing at first, and then decreases to 1.53 at a high doping ratio of 0.645. From the viewpoint of surface structure, the higher the content of Cu is, the rougher the surface is, since more cluster particles appear on the surface due to the small solid solubility of Cu in the amorphous carbon network. However, from viewpoint of the electronic structure, the reduction of the sp² hybrid bonds will increase the SEY effect as the content of Cu increases, due to the decreasing probability of collision with free electrons. Thus, the two mechanisms would compete and coexist to affect the SEY characteristics in Cu doped carbon films.     

通过光致还原调制氧化石墨烯寿命并用于微纳图形制备

氧化石墨烯因其宽带可调谐的荧光发射特性已被广泛应用于荧光成像、金属离子高灵敏检测和光电器件的制备.相比于荧光强度,氧化石墨烯荧光寿命不受材料厚度和激发功率的影响,具有更为稳定和均一的特性.本文研究了在激光还原过程中氧化石墨烯荧光寿命逐渐减小的变化行为,发现了长寿命sp~3杂化结构向短寿命sp~2杂化结构的转变.通过精确控制还原时间,结合激光直写技术,在单层氧化石墨烯薄膜上实现了二维码、条形码、图形和数字等微纳图形的制备,还在多层氧化石墨烯薄膜结构上获得了多寿命多层微纳图形.这种微纳图形的制备具有灵活无掩膜、高对比和多模式的特点,可用于高密度光学存储、信息显示和光电器件制备等诸多领域.     

含羟基结构熔石英光电性质的第一性原理研究

熔石英是高功率激光装置中广泛使用的激光透镜材料,采用第一性原理结合平面波赝势方法,研究了熔石英材料中羟基结构的生成模式,系统计算了材料的电子态密度、差分电荷密度、原子电荷布居分布,分析了包含羟基熔石英材料的光学跃迁模式,研究结果表明:熔石英中的三配位硅原子缺陷在禁带中生成了两条缺陷能级,分别位于7.8和8.8 eV;研究还发现氢原子与五配位硅原子发生相互作用生成羟基结构,该反应还使三配位硅原子的杂化方式由sp~2变为sp~3,这种羟基结构会影响体系的电子结构,使原有的7.8和8.8ev缺陷能级消失,并在费米面上生成一条半占据态缺陷能级,引起激发能为6.2 eV的光学跃迁。     

Metal-enhanced fluorescence of graphene oxide by palladium nanoparticles in the blue-green part of the spectrum

Graphene oxide(GO) has a wide fluorescence bandwidth,which makes it a prospective candidate for numerous applications.For many of these applications,the fluorescence yield of GO should be further increased.The sp~2-hybridized carbons in GO confine the π-electrons.Radiative recombination of electron-hole pairs in such sp~2 clusters is the source of fluorescence in this material.Palladium nanoparticles are good catalysts for sp~2 bond formations.We report on the preparation of GO,palladium nanoparticles and their nanocomposites in two different solvents.It is shown that palladium nanoparticles can considerably enhance the intrinsic fluorescence of GO in the blue-green part of the visible light spectrum.Fluorescence enhancement has been attributed to the catalytic role of palladium nanoparticles in increasing the number of sp2 bonds of GO with the molecules of the surrounding media.It is shown that palladium nanoparticles could be the nanoparticle of choice for fluorescence enhancement of GO because of their catalytic role in sp2 bond formation.     

白碳纳米晶薄膜及其场致电子发射特性

利用微波等离子体化学气相沉积方法,以甲烷、氢混合气体为反应气体,具有钛镀层的玻璃作为衬底,制备了具有sp¹杂化结构的白碳纳米晶薄膜。利用X射线衍射、俄歇电子能谱,以及扫描电子显微镜对薄膜结构进行了表征。以白碳纳米晶薄膜为阴极,以镀有ITO透明导电薄膜玻璃为阳极,采用二极管结构,测试了白碳纳米晶薄膜的场致电子发射特性。开启电场为2.5 V/μm,在电场为5 V/μm时的电流密度为200μA/cm²。对白碳纳米晶薄膜生长机理,以及其场致电子发射机制进行了讨论。     

β-SiC单晶块体拉伸变形行为分子动力学研究

用分子动力学方法研究面心立方SiC(β-SiC)、C元素置换掺杂β-SiC单晶块体体系[001]向拉伸变形行为,对体系的拉伸断裂微观机理和5×10⁸/s,1×10⁹/s,1×10¹⁰/s三种应变速率下的力学行为进行分析.发现当拉伸应变量达到某个临界值后,Si-C sp³,C-C sp³键会分别向Si-C sp²和C-C sp²弱键转化.形成一定量sp²键后,β-SiC内部出现孔洞并发生断裂.由于C-C sp³键比Si-C sp³键更易向sp²弱键转化,导致C元素掺杂会降低SiC的强度、弹性模量和拉伸断裂应变.此外还发现此三种应变速率不影响β-SiC的杨氏模量,但影响其拉伸强度.     

Al_2S_n~±(n=2—10)团簇结构特征和稳定性的密度泛函理论研究

采用密度泛函理论的B3LYP方法,在6-311G**水平上对Al2S±n(n=2—10)团簇的几何结构和电子结构进行了理论计算.讨论了铝硫二元离子混合团簇基态结构的变化规律、电荷转移和成键特征.结果表明,在S簇中掺杂Al原子会使Sn结构发生明显改变.Al2S±n团簇基态结构是以Al2S2四元环为骨架或桥梁,分别与S原子或S簇相结合形成单环到三环的平面和立体结构.结构中化学键键型和成键数目影响团簇的稳定性.通过对基态结构的解离能和能量二次差分值的分析得到了Al2S±n团簇的稳定性信息.     

非平衡磁控溅射制备类石墨碳膜及性能研究

利用中频非平衡磁控溅射技术在单晶硅基底上沉积了类石墨碳膜, 采用Raman光谱、高分辨透射电子显微镜、原子力显微镜分析了薄膜微观结构和表面形貌; 采用纳米压痕仪和CSM摩擦磨损试验机测试了碳膜力学性能和摩擦学性能. 结果表明: 利用中频非平衡磁控溅射技术沉积的碳膜是一种以sp²键合碳为主、结构非晶、硬度适中、应力较低、表面粗糙度较大、摩擦性能优异的薄膜. 脉冲占空比对薄膜微观结构和性能有显著影响, 随着脉冲占空比的增大, Raman光谱D峰和G峰的强度比I_D/I_G先减小后增大, 而硬度随脉冲占空比的增大却呈现出相反的变化趋势, 即先增大后减小; 大气氛围中的摩擦性能测试表明, 本实验制备的薄膜具有优异的抗磨性能(～10^-11 cm³/N^-1. m^-1)和承载能力(～2.5 GPa). 随脉冲占空比的增大, 薄膜摩擦系数变化甚微而磨损率却呈现先显著减小后轻微增大的变化趋势. 类石墨碳膜优异的摩擦学性能主要归因于其独特的结构、较低的内应力及良好的结构稳定性.     

Theory,preparation, properties and catalysis application in 2D graphynes-based materials

Carbon has three hybridization forms of sp⁻, sp²⁻ and sp³⁻, and the combination of different forms can obtain different kinds of carbon allotropes, such as diamond, carbon nanotubes, fullerene, graphynes (GYs) and graphdiyne (GDY). Among them, the GDY molecule is a single-layer two-dimensional (2D) planar structure material with highly π-conjugation formed by sp⁻ and sp²⁻ hybridization. GDY has a carbon atom ring composed of benzene ring and acetylene, which makes GDY have a uniformly distributed pore structure. In addition, GDY planar material have some slight wrinkles, which makes GDY have better self-stability than other 2D planar materials. The excellent properties of GDY make it attract the attention of researchers. Therefore, GDY is widely used in chemical catalysis, electronics, communications, clean energy and composite materials. This paper summarizes the recent progress of GDY research, including structure, preparation, properties and application of GDY in the field of catalysts.     

Laser-induced fluorescence experimental spectroscopy and theoretical calculations of uranium monoxide

As a model molecule of actinide chemistry, UO molecule plays an important role in understanding the electronic structure and chemical bonding of actinide-containing species. We report a study of the laser-induced fluorescence spectra of the U¹⁶O and U¹⁸O using two-dimensional spectroscopy. Several rotationally resolved excitation spectra were investigated. Accurate molecular rotational constants and equilibrium internuclear distances were reported. Low-lying electronic states information was extracted from high resolution dispersed fluorescence spectra and analyzed by the ligand field theory model. The configuration of the ground state was determined as U²⁺(5f³7s)O^2-. The branching ratios, and the vibrational harmonic and anharmonic parameters were also obtained. Radiative lifetimes were determined by recording the time-resolved fluorescence spectroscopy. Transition dipole moments were calculated using the branching ratios and the radiative lifetimes. These findings were elucidated by using quantum-chemical calculations, and the chemical bonding was also analyzed. The findings presented in this work will enrich our understanding of actinide-containing molecules.