Role of intermolecular interactions on the electronic and geometric structure of a large pi-conjugated molecule adsorbed on a metal surface

The organic semiconductor molecule 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) exhibits two adsorption states on the Ag(111) surface: one in a metastable disordered phase, prepared at low temperatures, the other in the long-range ordered monolayer phase obtained at room temperature. Notably, the two states differ substantial in their vertical bonding distances, intramolecular distortions, and electronic structures. The difference is explained by intermolecular interactions, which are particularly relevant for the long-range ordered phase, and which hence require attention.     

Shift and broadening of the vibrational mode for a diatomic molecule adsorbed on a metal surface

The shift and broadening of the vibrational frequency of a diatomic molecule adsorbed on a metal surface are calculated on the basis of electromagnetic interactions. Finite molecular size and nonlocal metal response are included in a calculation of the response function, whose pole is the complex normal mode frequency. Finite molecular size is described by a model of a point-like vibrational mode within a polarizable sphere. Nonlocal metal response is described by a semiclassical infinite barrier model with a Lindhard dielectric constant generalized to include core polarization and finite electron lifetime. When applied to the case of CO adsorbed on Cu and if the molecule is positioned so as to fit the observed width, it is found the predicted shift is a factor of three or more greater than that observed.     

扫描隧道显微镜针尖调制的薄膜表面的原子扩散

采用原子尺度的模拟方法,探讨了在零偏压下扫描隧道显微镜(STM)针尖调制的金属表面岛上原子运动及岛边的层间质量输运. 研究结果显示STM的移动对岛上及岛边的原子扩散有重要的影响. 针尖与吸附原子的交互作用及岛和基体中强的形状变化影响了岛上吸附原子的跳跃扩散及岛边的跳下扩散和交换扩散过程. 研究发现,通过调节针尖与基体的垂直距离及针尖与吸附原子的水平距离,可以降低岛上吸附原子的跳跃扩散能垒及岛边的跳下扩散和交换扩散能垒,从而实现薄膜由三维生长模式向二维生长模式的转变. 关键词： 扫描隧道显微镜 原子运动 质量输运     

Molecular distortions and chemical bonding of a large pi-conjugated molecule on a metal surface

Normal incidence x-ray standing wave experiments and density functional theory reveal that 3,4,9,10-perylene-tetracarboxylic-dianhydride chemisorbs on Ag(111) in a nonplanar but vertically distorted configuration. The carboxylic O atoms are 0.18 +/- 0.03 angstroms closer to the surface than the perylene core. The distortion is related to weak, local bonds between carboxylic O atoms and the Ag surface which are coupled--through charge transfer into the former lowest unoccupied molecular orbital--to the primary, extended chemisorption bond via the perylene skeleton.     

Imaging method of single layer graphene on metal substrate based on imaging ellipsometer with large field of view

Single layer lattice graphene deposited on the metal substrate can hardly be imaged by the optical microscope. In this Letter, a large field-of-view imaging ellipsometer is introduced to image single layer graphene which is deposited on a metal substrate. By adjusting the polarizer and the analyzer of imaging ellipsometer, the light reflected from surfaces of either single layer graphene or a Au film substrate can be extinguished, respectively.Thus, single layer graphene can be imaged correspondingly under brightfield or darkfield imaging modes. The method can be applied to imaging large-area graphene on a metal substrate.     

Growth and transport properties of topological insulator Bi_2Se_3 thin film on a ferromagnetic insulating substrate

Exchange coupling between topological insulator and ferromagnetic insulator through proximity effect is strongly attractive for both fundamental physics and technological applications. Here we report a comprehensive investigation on the growth behaviors of prototype topological insulator Bi_2Se_3 thin film on a single-crystalline LaCoO_3 thin film on SrTiO_3 substrate, which is a strain-induced ferromagnetic insulator. Different from the growth on other substrates, the Bi_2Se_3 films with highest quality on LaCoO_3 favor a relatively low substrate temperature during growth. As a result, an inverse dependence of carrier mobility with the substrate temperature is found. Moreover, the magnetoresistance and coherence length of weak antilocalization also have a similar inverse dependence with the substrate temperature, as revealed by the magnetotransport measurements. Our experiments elucidate the special behaviors in Bi_2Se_3/LaCoO_3 heterostructures,which provide a good platform for exploring related novel quantum phenomena, and are inspiring for device applications.     

有机分子吸附和衬底调控锗烯的电子结构

锗基集成电子学的发展潜力源于其极高的载流子迁移率以及与现有的硅基和锗基半导体工业的兼容性,而锗烯微小带隙能带特点极大程度地阻碍其应用.因此,在不降低载流子迁移率的情况下,打开一个相当大的带隙是其应用于逻辑电路中首先要解决的问题.本文采用范德瓦耳斯力修正的密度泛函理论计算方法,研究了电场作用下有机分子吸附和衬底对锗烯原子结构和电学性质的影响.研究结果表明,有机分子吸附和衬底通过弱相互作用破坏了锗烯亚晶格的对称性,从而在狄拉克点上打开了相当大的带隙.苯/锗烯和六氟苯/锗烯体系均在K点打开了带隙.当使用表面完全氢化的锗烯(锗烷HGeH)衬底时,苯/锗烯/HGeH和六氟苯/锗烯/HGeH体系的带隙可进一步变宽,带隙值分别为0.152和0.105 eV.在外电场作用下,上述锗烯体系可实现大范围的近似线性可调谐带隙.更重要的是,载流子迁移率在很大程度上得以保留.本文提出了一种有效的可调控锗烯带隙的设计方法,为锗烯在场效应管和其他纳米电子学器件中的应用提供了重要的理论指导.     

Raman spectral detection and assessment of thin organic layers on metal substrates: systematic approach from substrate preparation to map evaluation

Raman spectral mapping of thin organic layers on metal substrates is an important analytical tool to characterize these systems. Surface‐enhanced Raman scattering (SERS) spectroscopy is a suitable technique for analysis of such layers. Development of new SERS‐active surfaces with repeatable properties and without disturbing adsorbed species is one of the important steps for reliable assessment of the thin organic layers designed. This paper presents new SERS‐active substrates suitable for both macro (millimeter scale) and microscopic (micrometer scale) spectral mapping, which allow easy regeneration for repetitive experiments. Both gold and silver SERS‐active surfaces prepared by electrochemical deposition were tested. Complete map data evaluation utilities were newly designed and applied, using both ordinarily used and newly modified mathematical algorithms and chemometric procedures. Evaluation of data starts with finite impulse response (FIR) filtration algorithms to eliminate spectral interferences in individual spectra. Principal component analysis was used for transformation of multidimensional data to understandable dimensions. Various mathematical/statistical techniques were then used for data visualization as spectral maps and for similarity testing. Copyright © 2008 John Wiley & Sons, Ltd.     

A near perfect Pendry lens: Projecting properties of a thin metal layer

We consider the field of an evanescent wave in a space with a thin metal layer (? < 0). The wavenumber of the evanescent wave appreciably exceeds the wavenumber k ₀ = 2π/λ₀ of a uniform plane wave in spatial regions adjacent to the metal. In accordance with the Pendry result (2000), the field behind the metal layer is amplified as compared to the field in the absence of the layer. Pendry predicted this effect for a metal whose dielectric permittivity is ? = ?1, whereas we show that the effect can also be observed for ? = ?15 and for arbitrarily thick adjacent regions. This extends the range of possible applications of the effect. We find that the losses in the metal only weakly affect the image quality behind the metal layer.     

Martensitic transformations in a thin layer of a shape memory alloy on an elastic substrate

A martensitic transformation (MT) in a thin (10–10³ nm thick) layer of a shape memory alloy on an elastic substrate is analyzed theoretically in terms of the theory of diffuse MTs. The relaxation of thermoelastic stresses associated with the MT is considered, and the size effects that accompany this relaxation are analyzed; stresses arise in the layer because of the difference in the coefficients of thermal expansion of the materials of the microcomposite. It is found that nonlinear and hysteretic properties are imparted by the MT to microdrives (actuators) and temperature-sensitive microelements based on such composites.     

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.     

Effect of a thin dielectric layer on terahertz transmission characteristics for metal hole arrays

We studied the role of surface-plasmon polaritons (SPPs) in a bandpass transmission property of two-dimensional metal hole arrays (2D-MHAs) by investigating the effect of thin dielectric layers on the 2D-MHA surfaces. We measured zero-order transmission spectra of the 2D-MHAs by changing the thickness of the dielectric layer and found that the bandpass transmission peak shifted to the lower-frequency side with increasing layer thickness, owing to the change of the resonant frequency of the SPP. This result shows that SPPs play a crucial role in the transmission property of 2D-MHAs in the terahertz region.     

A direct determination of acoustical impedance of a thin layer on a thick elastic substrate by the ultrasound

A direct determination method of acoustical impedance of a linear-viscoelastic thin layer on a thick elastic substrate is proposed without the prior knowledge of other layer parameters. With the rectangular windows that start at the time zero and are rightward expanded, the successive windowing operations on the total ultrasonic reflected signals are performed. Using the transfer functions of the windowed signals and the analytical formula, the distribution characteristic of the calculated results of acoustical impedance with the different frequency intervals and the behavior of the corresponding estimated values are numerically investigated as the lengths of the sampling windows change. Acoustical impedance of the thin layer can be directly determined from the distribution characteristic of the calculated results and the behavior of the estimated values. The proposed direct determination method is independent of the parameters of the next substrates.     

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.     

UV desorption and photochemistry of dimethylgold hexafluoroacetylacetonate adsorbed on a quartz substrate

The photodesorption and photodecomposition pathways of dimethylgold hexafluoroacetylacetonate, DMG (hfac), adsorbed on a cooled quartz substrate is reported for 222-nm KrCl excimer laser radiation. The time-of-flight (TOF) of neutral photoproducts, desorbed from the surface of the gold film formed during the experiment, were analyzed under collisionless conditions by a differentially-pumped mass spectrometer. Extensive dissociation of adsorbed DMG (hfac) into DMG and the hfac ligand was observed. The ligand was found to recombine with a CH₃ radical on the surface. Translational energy distributions for the detected species were obtained by deconvoluting the TOF curves into a self-consistent set of Maxwell-Boltzmann distributions for the desorbed parent molecule, laser-induced decomposition products, and surface recombination reaction products. The implications of these results for the mechanistic details of the low-pressure, laser-assisted organometallic deposition of DMG(hfac) are discussed.ONT/NRL Research Associate (Nov. 1987-Oct. 1988)NRC/NRL Cooperative Research Associate     

Influence of the metal substrate on the adsorption properties of thin oxide layers: Au atoms on a thin alumina film on NiAl(110)

Thin oxide films grown on metal substrates are widely used in surface science to model bulk oxides, assuming their chemical and electronic properties to be similar. In some cases, however, this might not be justified as the present scanning tunneling microscopy studies demonstrate for Au atoms on a thin alumina film on NiAl(110). Au atoms were evaporated onto the oxide film at a sample temperature of approximately 10 K. At low coverage, this leads to the formation of one-dimensional clusters with unusually large Au-Au distances of 5.6-6.0 A. A direct interaction between the Au atoms can be excluded, and a substrate-mediated mechanism is supposed instead. This assumption is strengthened by the finding that the Au chains exhibit a preferential orientation: They are almost aligned with the [001] direction of the NiAl(110) substrate, clearly indicating that the metal substrate participates in the binding of the Au atoms.     

AlGaN插入层对6H-SiC上金属有机物气相外延生长的GaN薄膜残余应力及表面形貌的影响

研究了具有不同台阶数目的AlGaN插入层对在6H-SiC衬底上利用金属有机物气相外延（MOVPE）生长的GaN体材料残余应力和表面形貌的影响.高分辨率X射线衍射测试表明样品的c轴晶格常数随台阶数目的增多而增大;低温光荧光谱中GaN发光峰也随着台阶数目增多而发生蓝移,这些变化都反映出GaN中残余张应力的减小.此外,原子力显微镜测试表明样品表面起伏和粗糙度也都随着插入层的引入和台阶数目的增多得到了明显的改善. 关键词： 残余应力 表面形貌 SiC衬底 AlGaN插入层