Raman-STM联用系统及其初步实验

研究固／液界面体系的传统方法主要以电信号为激励和检测手段，已不能适应日益扩大的研究对象和深入至微观研究的要求，许多采用电子束或离子束作为人射源的表面技术由于x作在高真空条件下也难以原位（insitu）研究固／液体表由于光束容易穿过团／液体系的溶液层或具有光学透明的固体电极材料，八十年代以来以光（尤其是激光）作为激励和检测手段的研究方法日益受到重视[1]，目前已开展的工作包括光电流（电压、电容）谱、光发射电流话、光声（热）谱、反（透）射谱、全息谱、瑞利散射、（超）拉曼散射、二次谐波（SHG）以及和频（SFG）…     

The puzzle of contrast inversion in DNA STM imaging

DNA has been at the center of an imaging effort since the invention of the scanning tunneling microscope (STM). In some of the STM imaging reports the molecules appeared with negative contrast, i.e., "submerged" under the metal background and darker. We demonstrate the phenomenon of contrast inversion in DNA STM imaging by controlled and spontaneous contrast inversions and by the dependence of the DNA apparent height with respect to the surface on the imaging bias voltage. Using these characterizations, we formulate a model explaining the above phenomenon by resonant tunneling through virtual states in the vacuum between the STM tip and the DNA molecule.     

A dodecameric porphyrin wheel

A dodecameric porphyrin wheel was prepared by Ag(I)-promoted intramolecular coupling of a linear porphyrin dodecamer and was observed by scanning tunneling microscopy (STM). Efficient energy hopping along the array was revealed by femtosecond transient anisotropy measurements.     

Molecular Spoked Wheels: Synthesis and Self‐Assembly Studies on Rigid Nanoscale 2D Objects

We present the efficient synthesis of a new molecular spoked‐wheel structure ( MSW‐3 ). Two derivatives with diameters of approximately 4 nm have been prepared. By highlighting the importance of pseudo‐high‐dilution conditions during cyclization, we were able to access the compounds on a several hundred milligram scale. In addition to the standard characterization (NMR spectroscopy, MS), we describe a detailed investigation of the optical properties of the fluorescent MSWs by comparison with appropriate model chromophores. Furthermore, a comprehensive study of the structure in solution by means of light‐ and X‐ray scattering experiments has been conducted. Scanning tunneling microscopy (STM) revealed the two‐dimensional organization of the molecules on highly oriented pyrolytic graphite and emphasized the spoked‐wheel structure. The diameter of these molecules measured by small‐angle X‐ray scattering is in very good agreement with that obtained from STM and matches the results of molecular modeling. This confirms the rigidifying effect of the spokes, which results in highly shape‐persistent nanometer‐sized oblate organic compounds.     

Dispersion and STM Characterization of Au-CdSe Nanohybrids on Au(111)

We report the dispersion and scanning tunneling microscopy (STM) characterization of iso-lated Au-CdSe nanohybrids on atomically flat Au(111) through surface modifications. The top terminal groups of spacer molecules self-assembled on the surface are found critical for locking the nanohybrids into a well-separated state. The STM results indicate that both thiol and carboxylic terminals are effective in this aspect by making strong interaction with the Au portions of the nanohybrids. An argon ion sputtering technique is also proposed to clean up organic contaminants on the surface for improved STM imaging of individual Au-CdSe nanohybrids. These observations help to enrich technical approaches to dispersing individual nanostructures on the surface and provide opportunities to explore their local electroluminescent and energy transfer properties at the nanoscale.     

Multiscale imaging and tip-scratch studies reveal insight into the plasma oxidation of graphite

The plasma oxidation process of highly oriented pyrolytic graphite (HOPG) has been investigated through a combination of multiscale (micrometric to atomic) imaging by atomic force and scanning tunneling microscopies (AFM/STM) and STM tip-scratching of the HOPG substrate. Complementary information was obtained by Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). Repetitive imaging of the same HOPG location following a series of consecutive plasma treatments allowed an accurate determination of the plasma etch rates along both the a and c crystallographic directions of the graphite lattice. The etch rates were typically in the range of a few nm per min along the a axis, and the equivalent of 1-6 graphene layers per min along the c axis. The results pointed to the existence of two main plasma etching regimes, related to short (<20-30 min) and long (> or =30 min) treatment times. This was inferred not only from the measured plasma etch rates but also from the observation of fundamental differences in the atomic-scale surface structure of the plasma-treated HOPG samples, and from the general mechanical behavior of the materials under the action of the AFM tip. In particular, atomic-scale STM imaging suggested a change from a defected, but essentially graphitic, surface in the first regime to an amorphous carbon surface in the second regime. Together with AFM and STM, Raman spectroscopy and XPS provided a consistent picture of the surface structure and chemistry of the plasma-modified HOPG in the two regimes. The implications of these results as well as the possible mechanism that drives the plasma etching process in the two regimes are discussed.     

Challenges and errors: interpreting high resolution images in scanning tunneling microscopy

With the availability of first principles methods to simulate the operation of a scanning tunneling microscope (STM) theory has moved from the qualitative and topographic to the quantitative and dynamic. Simulations in effect predict the influence of a model-tip or chemical interactions between tip and sample in the actual imaging process. By comparing experiments and simulations, the information about the analyzed system can be substantially extended. We give an overview of recent work, where the combination of first principles simulations with high resolution measurements was decisive to arrive at consistent results. This concerns the resolution of single wavefunctions by STM, force effects in high resolution scans, contrast reversal due to the field of the tip, the imaging of magnetic properties by spin-polarized STM, and the analysis of dynamic processes on surfaces.     

Chemically resolved scanning tunneling microscopy imaging of Al on p-type Al0.1Ga0.9As(001)-c(2x8)(2x4)

The ability to chemically differentiate individual subsurface Al and Ga atoms, when imaging the Al0.1Ga0.9As(001)-c(2x8)(2x4) surface with scanning tunneling microscopy (STM), has been observed for the first time. In filled-state STM images first layer As atoms bonded to second layer Al atoms appear brighter than those bonded to second layer Ga atoms. This effect is only observed experimentally with p-type Al0.1Ga0.9As grown on p-type GaAs substrates and has been computationally modeled with density functional theory (DFT) calculations. It is hypothesized that chemical specificity is not observed on n-type material because the extra surface charge given to first layer As atoms by second layer Al atoms adds negligibly to the filled-state density of the surface, thus preventing the visualization of chemical specificity with filled-state STM imaging. The ability to distinguish whether first layer As atoms are bonded to second layer Ga and/or Al atoms in STM images shows that small differences in bond ionicity affect the local electronic structure of the material.     

Bias-dependent visualization of electron donor (D) and electron acceptor (A) moieties in a chiral DAD triad molecule

The 2D crystal lattice structure and bias-dependent contrast of a chiral electron donor-acceptor-donor triad system, composed of two oligo(p-phenylene vinylene) electron donors and a perylenediimide electron acceptor (OPV4-PDI-OPV4), have been studied by means of scanning tunneling microscopy (STM) at the liquid-graphite interface. OPV4-PDI-OPV4 is ordered in rows and forms a well-ordered 2D crystal lattice structure. The electrical properties of the donor and acceptor parts are distinguished by the contrast in bias-dependent STM imaging.     

四苯基卟啉铜分子的扫描隧道显微镜成像

本文首次以ＬＢ技术将四苯基卟啉铜（ＣｕＴＰＰ）分子沉积到高定向热解石墨上，并用ＳＴＭ研究其表面形貌，得到了原子级分辨的ＣｕＴＰＰ分子的表面形貌图，结果表明，ＣｕＴＰＰ分子具有近似圆状平面结构，分子直径为１．０ｎｍ，与理论结果十分吻合，结合ＳＴＭ原理，讨论了有机大分子ＳＴＭ成像的条件。     

Role of the anion in the underpotential deposition of cadmium on a Rh(111) electrode: probed by voltammetry and in situ scanning tunneling microscopy

In situ scanning tunneling microscopy (STM) and cyclic voltammetry (CV) were employed to examine the underpotential deposition (UPD) of cadmium on a rhodium(111) electrode in sulfuric and hydrochloric acids. The (bi)sulfate and chloride anions in the electrolytes played a main role in controlling the number and arrangement of Cd adatoms. Deposition of Cd along with hydrogen adsorption occurred near 0.1 V (vs reversible hydrogen electrode) in either 0.05 M H2SO4 or 0.1 M HCl containing 1 mM Cd(ClO4)2. These coupled processes resulted in an erroneous coverage of Cd adatoms. The process of Cd deposition shifted positively to 0.3 V and thus separated from that of hydrogen in 0.05 M H2SO4 containing 0.5 M Cd2+. The amount of charge (80 microC/cm2) for Cd deposition in 0.5 M Cd2+ implied a coverage of 0.17 for the Cd adatoms, which agreed with in situ STM results. Regardless of [Cd2+], in situ STM imaging revealed a highly ordered Rh(111)-(6 x 6)-6Cd + HSO4- or SO42- structure in sulfuric acid,. In hydrochloric acid, in situ STM discerned a (2 x 2)-Cd + Cl structure at potentials where Cd deposition commenced. STM atomic resolution showed roughly one-quarter of a monolayer of Cd adatoms were deposited, ca. 50% more than in sulfuric acid. Dynamic in situ STM imaging showed potential dependent, reversible transformations between the (6 x 6) Cd adlattices and (square root 3 x square root 7)-(bi)sulfate structure, and between (2 x 2) and (square root 7 x square root 7)R19.1 degrees -Cl structures. The fact that different Cd structures observed in H2SO4 and HCl entailed the involvement of anions in Cd deposition, i.e. (bi)sulfate and chloride anions were codeposited with Cd adatoms on Rh(111).     

High-resolution STM imaging of novel poly(G)-poly(C) DNA molecules

High-resolution scanning tunneling microscopy (STM) imaging of single double-stranded poly(G)-poly(C) DNA molecules, made by a novel synthesis method, shows the molecules morphology. The STM images reveal a periodic structure of approximately 4 nm, seen as repeating "bulbs" along the molecules. These "bulbs" are associated with the molecule helix (the major grooves). "Nicks", two per 100 nm on the average, are observed along the DNA as well. The STM measurements were supported by a morphological statistics of the DNA molecule groove length and apparent height relative to the surface.     

Rastertunnelmikroskopie an chiralen Molekülen: Nanochemie

The imaging and manipulation capabilities of the scanning tunnelling microscope (STM) render possible a novel nanoscale chemistry based on experiments with single molecules. Herein, we address several aspects of a nanoscale stereochemistry using the STM. As an example, we investigate 1‐nitronaphthalene on Au(111). 1‐Nitronaphthalene becomes chiral upon planar adsorption on the metal surface. High‐resolution STM images reflect the asymmetric electronic structure of the molecules and allow for the determination of the absolute configuration of any individual molecule within complex molecular structures. At medium coverage, spontaneous breaking of the chiral symmetry results in the formation of homochiral conglomerates, while at high coverage racemic structures prevail. Finally, the tip of the STM is used to separate “supramolecule‐by‐supramolecule” a racemic mixture of chiral 1‐nitronaphthalene aggregates into the enantiopure compounds.     

Synthesis,separation, and isomer-dependent packing in two dimensions--detected by scanning tunnelling microscopy--of a TTF derivative

The synthesis, isolation and STM imaging on graphite of the cis and trans isomers of a TTF reveal isomer-dependent packing, and constitutes a way to study the non-covalent interactions at play in these systems.     

UHV STM I(V) and XPS studies of aryl diazonium molecules assembled on Si(111)

Molecular layers formed from 4-trifluoromethylbenzenediazonium tetrafluoroborate and 4-Methylbenzenediazonium tetrafluoroborate have been assembled on H-passivated Si(111) and studied by UHV STM and XPS. STM imaging shows well-developed Si(111) step edges and terraces both on Si(111):H and Si(111) substrates covered with a molecular layer. STM I(V) data acquired at different tip-substrate separations reveals a factor of approximately 10 enhancement in current for positive bias voltage when current flows through the 4-trifluoromethyl molecule when compared to the 4-methyl variant. The observed current enhancement in I(V) can be understood by comparing the projected density of states of the two molecule-Si systems calculated using a density functional theory local density approximation after geometry optimization was performed via the conjugate gradient method. XPS data independently confirm that H-passivated Si(111) remains oxygen free for short exposures to ambient conditions and provide evidence that the molecules chemically react with the silicon surface.     

单细胞成像观测研究进展

综述了近几年各种研究手段如STM,AFM和NOSM等在单细胞成像观测方面的研究进展,并对细胞成像观测的历史、现状及发展趋势作了综述。     

STM imaging of a heptanuclear ruthenium(II) dendrimer, mono-add layer on graphite

Scanning tunneling microscopy (STM) and molecular mechanics calculations were used to investigate the long-range packing and the structure of an heptanuclear ruthenium (II) dendritic species, as a PF6- salt. STM imaging was carried out on a mono-add layer of the ruthenium dendrimer formed by physisorption from a 1,2,4-trichlorobenzene solution at the liquid-graphite interface. The packing of the molecules on the surface was visualised by the formation of ordered patterns and a distance of 27 +/- 2 A was measured between two adjacent lamellae. The comparison of this dimension with the molecular-modelling data indicates that the lamellae were formed by rows of dendrimer molecules in which the counterions (PF6-) were strongly associated with the Ru atoms. The images acquired with higher spatial resolution revealed the presence of repeating units within the lamellae. The comparison of the STM images with the modelling results allowed the attribution of the repeating units observed in the imaged pattern to the STM signature of single dendrimer molecules.     

Metal–organic interaction probed by First Principles STM simulations

The Review is devoted to recent progress made from the combination of Scanning Tunneling Microscope (STM) experiments and First Principles atomistic simulations in the chemical characterization of metal–organic interfaces. Density Functional Theory (DFT) has now reached the point to mimic in a quantitative way two pillars of the STM probe: the imaging mode convoluting the topographic and electronic properties and the spectroscopy modes comprising of elastic and inelastic detection ways. We present a selection of hybrid interfaces ranging from isolated benzene derivatives to thin honeycomb carbon film – a single graphene layer – deposited onto transition metal surfaces. The direct experimental analysis of these interfaces was error-prone, necessitating the confrontation with First Principles atomistic simulations. The few examples thus illustrate the power of different kinds of STM simulations to complement the STM data, in order to unambiguously identify the chemical structure of organic adsorbates.     

Noncontact to contact tunneling microscopy in self-assembled monolayers of alkylthiols on gold

The mechanical interaction between a scanning tunneling microscopy (STM) probe and hexadecane (C16) alkylthiol molecules in a self-assembled monolayer was investigated by sensing the force during constant current mode STM imaging. The force regime changed from attractive to repulsive over the insulating molecule islands under feedback control of the current. The repulsive force on the molecule was strongly dependent on the setpoint value of the current during STM operation. In our experiments, the threshold for contact was found at a tunneling current of 1 pA when the sample bias is 2 V. At higher current, the apparent height of molecular islands changed logarithmically with current. In addition, the current as a function of applied load revealed a stepwise increase, indicative of discrete molecular tilting events. A tunneling decay constant beta of =0.53+/-0.02 A(-1) was obtained based on the measurement of the height of molecules and the tunneling current.