Nanomechanical oscillations in a single-C60 transistor

The motion of electrons through quantum dots is strongly modified by single-electron charging and the quantization of energy levels. Much effort has been directed towards extending studies of electron transport to chemical nanostructures, including molecules, nanocrystals and nanotubes. Here we report the fabrication of single-molecule transistors based on individual C60 molecules connected to gold electrodes. We perform transport measurements that provide evidence for a coupling between the centre-of-mass motion of the C60 molecules and single-electron hopping--a conduction mechanism that has not been observed previously in quantum dot studies. The coupling is manifest as quantized nano-mechanical oscillations of the C60 molecule against the gold surface, with a frequency of about 1.2 THz. This value is in good agreement with a simple theoretical estimate based on van der Waals and electrostatic interactions between C60 molecules and gold electrodes.     

Coulomb blockade and the Kondo effect in single-atom transistors

Using molecules as electronic components is a powerful new direction in the science and technology of nanometre-scale systems. Experiments to date have examined a multitude of molecules conducting in parallel, or, in some cases, transport through single molecules. The latter includes molecules probed in a two-terminal geometry using mechanically controlled break junctions or scanning probes as well as three-terminal single-molecule transistors made from carbon nanotubes, C(60) molecules, and conjugated molecules diluted in a less-conducting molecular layer. The ultimate limit would be a device where electrons hop on to, and off from, a single atom between two contacts. Here we describe transistors incorporating a transition-metal complex designed so that electron transport occurs through well-defined charge states of a single atom. We examine two related molecules containing a Co ion bonded to polypyridyl ligands, attached to insulating tethers of different lengths. Changing the length of the insulating tether alters the coupling of the ion to the electrodes, enabling the fabrication of devices that exhibit either single-electron phenomena, such as Coulomb blockade, or the Kondo effect.     

Measurement of the conductance of a hydrogen molecule

Recent years have shown steady progress towards molecular electronics, in which molecules form basic components such as switches, diodes and electronic mixers. Often, a scanning tunnelling microscope is used to address an individual molecule, although this arrangement does not provide long-term stability. Therefore, metal-molecule-metal links using break-junction devices have also been explored; however, it is difficult to establish unambiguously that a single molecule forms the contact. Here we show that a single hydrogen molecule can form a stable bridge between platinum electrodes. In contrast to results for organic molecules, the bridge has a nearly perfect conductance of one quantum unit, carried by a single channel. The hydrogen bridge represents a simple test system in which to understand fundamental transport properties of single-molecule devices.     

Kondo resonance in a single-molecule transistor

When an individual molecule, nanocrystal, nanotube or lithographically defined quantum dot is attached to metallic electrodes via tunnel barriers, electron transport is dominated by single-electron charging and energy-level quantization. As the coupling to the electrodes increases, higher-order tunnelling and correlated electron motion give rise to new phenomena, including the Kondo resonance. To date, all of the studies of Kondo phenomena in quantum dots have been performed on systems where precise control over the spin degrees of freedom is difficult. Molecules incorporating transition-metal atoms provide powerful new systems in this regard, because the spin and orbital degrees of freedom can be controlled through well-defined chemistry. Here we report the observation of the Kondo effect in single-molecule transistors, where an individual divanadium molecule serves as a spin impurity. We find that the Kondo resonance can be tuned reversibly using the gate voltage to alter the charge and spin state of the molecule. The resonance persists at temperatures up to 30 K and when the energy separation between the molecular state and the Fermi level of the metal exceeds 100 meV.     

A nanometre-scale electronic switch consisting of a metal cluster and redox-addressable groups

So-called bottom-up fabrication methods aim to assemble and integrate molecular components exhibiting specific functions into electronic devices that are orders of magnitude smaller than can be fabricated by lithographic techniques. Fundamental to the success of the bottom-up approach is the ability to control electron transport across molecular components. Organic molecules containing redox centres-chemical species whose oxidation number, and hence electronic structure, can be changed reversibly-support resonant tunnelling and display promising functional behaviour when sandwiched as molecular layers between electrical contacts, but their integration into more complex assemblies remains challenging. For this reason, functionalized metal nanoparticles have attracted much interest: they exhibit single-electron characteristics (such as quantized capacitance charging) and can be organized through simple self-assembly methods into well ordered structures, with the nanoparticles at controlled locations. Here we report scanning tunnelling microscopy measurements showing that organic molecules containing redox centres can be used to attach metal nanoparticles to electrode surfaces and so control the electron transport between them. Our system consists of gold nanoclusters a few nanometres across and functionalized with polymethylene chains that carry a central, reversibly reducible bipyridinium moiety. We expect that the ability to electronically contact metal nanoparticles via redox-active molecules, and to alter profoundly their tunnelling properties by charge injection into these molecules, can form the basis for a range of nanoscale electronic switches.     

Field regulation of single-molecule conductivity by a charged surface atom

Electrical transport through molecules has been much studied since it was proposed that individual molecules might behave like basic electronic devices, and intriguing single-molecule electronic effects have been demonstrated. But because transport properties are sensitive to structural variations on the atomic scale, further progress calls for detailed knowledge of how the functional properties of molecules depend on structural features. The characterization of two-terminal structures has become increasingly robust and reproducible, and for some systems detailed structural characterization of molecules on electrodes or insulators is available. Here we present scanning tunnelling microscopy observations and classical electrostatic and quantum mechanical modelling results that show that the electrostatic field emanating from a fixed point charge regulates the conductivity of nearby substrate-bound molecules. We find that the onset of molecular conduction is shifted by changing the charge state of a silicon surface atom, or by varying the spatial relationship between the molecule and that charged centre. Because the shifting results in conductivity changes of substantial magnitude, these effects are easily observed at room temperature.     

Coulomb-blockade transport in single-crystal organic thin-film transistors

Coulomb-blockade transport--whereby the Coulomb interaction between electrons can prohibit their transport around a circuit--occurs in systems in which both the tunnel resistance, Rb between neighbouring sites is large (>h/e2) and the charging energy, E(C) (E(C) = e2/2C, where C is the capacitance of the site), of an excess electron on a site is large compared to kT. (Here e is the charge of an electron, k is Boltzmann's constant, and h is Planck's constant.) The nature of the individual sites--metallic, superconducting, semiconducting or quantum dot--is to first order irrelevant for this phenomenon to be observed. Coulomb blockade has also been observed in two-dimensional arrays of normal-metal tunnel junctions, but the relatively large capacitances of these micrometre-sized metal islands results in a small charging energy, and so the effect can be seen only at extremely low temperatures. Here we demonstrate that organic thin-film transistors based on highly ordered molecular materials can, to first order, also be considered as an array of sites separated by tunnel resistances. And as a result of the sub-nanometre sizes of the sites (the individual molecules), and hence their small capacitances, the charging energy dominates at room temperature. Conductivity measurements as a function of both gate bias and temperature reveal the presence of thermally activated transport, consistent with the conventional model of Coulomb blockade.     

Dependence of single-molecule junction conductance on molecular conformation

Since it was first suggested that a single molecule might function as an active electronic component, a number of techniques have been developed to measure the charge transport properties of single molecules. Although scanning tunnelling microscopy observations under high vacuum conditions can allow stable measurements of electron transport, most measurements of a single molecule bonded in a metal-molecule-metal junction exhibit relatively large variations in conductance. As a result, even simple predictions about how molecules behave in such junctions have still not been rigorously tested. For instance, it is well known that the tunnelling current passing through a molecule depends on its conformation; but although some experiments have verified this effect, a comprehensive mapping of how junction conductance changes with molecular conformation is not yet available. In the simple case of a biphenyl--a molecule with two phenyl rings linked by a single C-C bond--conductance is expected to change with the relative twist angle between the two rings, with the planar conformation having the highest conductance. Here we use amine link groups to form single-molecule junctions with more reproducible current-voltage characteristics. This allows us to extract average conductance values from thousands of individual measurements on a series of seven biphenyl molecules with different ring substitutions that alter the twist angle of the molecules. We find that the conductance for the series decreases with increasing twist angle, consistent with a cosine-squared relation predicted for transport through pi-conjugated biphenyl systems.     

Electrically driven directional motion of a four-wheeled molecule on a metal surface

Propelling single molecules in a controlled manner along an unmodified surface remains extremely challenging because it requires molecules that can use light, chemical or electrical energy to modulate their interaction with the surface in a way that generates motion. Nature's motor proteins have mastered the art of converting conformational changes into directed motion, and have inspired the design of artificial systems such as DNA walkers and light- and redox-driven molecular motors. But although controlled movement of single molecules along a surface has been reported, the molecules in these examples act as passive elements that either diffuse along a preferential direction with equal probability for forward and backward movement or are dragged by an STM tip. Here we present a molecule with four functional units--our previously reported rotary motors--that undergo continuous and defined conformational changes upon sequential electronic and vibrational excitation. Scanning tunnelling microscopy confirms that activation of the conformational changes of the rotors through inelastic electron tunnelling propels the molecule unidirectionally across a Cu(111) surface. The system can be adapted to follow either linear or random surface trajectories or to remain stationary, by tuning the chirality of the individual motor units. Our design provides a starting point for the exploration of more sophisticated molecular mechanical systems with directionally controlled motion.     

非Born—Oppenheimer近似(Ⅱ)——广义Berlin面

本文用非Born—Oppenheimer近似修改了双原子分子的Berlin面方程,从而电子的“束缚区”和“反束缚区”不仅与原子核的电荷和振动能级有关,而且还与核的质量和所有的电子在多维空间中的平均位置随核间距离的变化率有关。     

Single crystals of an ionic anthracene aggregate with a triplet ground state

Crystalline supramolecular aggregates consisting of charged organic molecules, held together through metal-cluster-mediated Coulomb interactions, have attracted interest owing to their unusual structural, chemical and electronic properties. Aggregates containing metal cation clusters 'wrapped' by lipophilic molecular anions have, for example, been shown to be kinetically stable and soluble in nonpolar liquids such as saturated hydrocarbons. The formation of supramolecular aggregates can even be exploited to generate aromatic hydrocarbons that carry four negative charges and crystallize in the form of organic poly(metal cation) clusters or helical polymers. Here we report the anaerobic crystallization of an ionic organic aggregate--a contact ion septuple consisting of a fourfold negatively charged 'tripledecker' of three anthracene molecules bridged by four solvated potassium cations. Its electronic ground state is shown experimentally, using temperature-dependent electron paramagnetic resonance spectroscopy, to be a triplet. Although the spins in this biradical ionic solid are separated by a considerable distance, density functional theory calculations indicate that the triplet ground state is 84 kJ mol(-1) more stable than the first excited singlet state. We expect that the successful crystallization of the ionic solid we report here, and that of a covalent organic compound with a triplet ground state at room temperature, will stimulate further attempts to develop new triplet-ground-state materials for practical use.     

单分子二极管整流特性的第一性原理计算

在分子电子学领域中, 设计分子的结构可以实现特定的功能. 单分子二极管的整流行为是极具吸引力的器件功能之一. 研究了对称分子和非对称分子结的电子输运, 分别对应为四苯基和二嘧啶基二苯基单分子结, 二者均是共价结合到两金属电极. 与其同源对称嵌段相比, 非对称二嵌段分子表现出明显的整流行为, 且电子输运方向是从二苯基流向二嘧啶基. 利用密度泛函理论(density functional theory, DFT)和非平衡格林函数(non-equilibrium Green's function, NEGF)结合的第一性原理方法研究了单分子结的电子结构及其量子输运. 电流-电压 ($I$-$V$)曲线的非对称性可以用非对称分子二嵌段在偏压下由于电子态的局域性带来的非平衡效应进行解释. 本理论计算定性上符合其他小组的实验结果, 且尝试了不同的末端接触. 结果发现, 实验中的扫描隧道显微镜(scanning tunneling microscope, STM)针尖接触结构会一定程度地抵消非对称分子的整流效应, 而 STM 针尖接触结构的结果分析也符合之前的理论预测.     

Self-assembled monolayer organic field-effect transistors

The use of individual molecules as functional electronic devices was proposed in 1974 (ref. 1). Since then, advances in the field of nanotechnology have led to the fabrication of various molecule devices and devices based on monolayer arrays of molecules. Single molecule devices are expected to have interesting electronic properties, but devices based on an array of molecules are easier to fabricate and could potentially be more reliable. However, most of the previous work on array-based devices focused on two-terminal structures: demonstrating, for example, negative differential resistance, rectifiers, and re-configurable switching. It has also been proposed that diode switches containing only a few two-terminal molecules could be used to implement simple molecular electronic computer logic circuits. However, three-terminal devices, that is, transistors, could offer several advantages for logic operations compared to two-terminal switches, the most important of which is 'gain'-the ability to modulate the conductance. Here, we demonstrate gain for electronic transport perpendicular to a single molecular layer ( approximately 10-20 A) by using a third gate electrode. Our experiments with field-effect transistors based on self-assembled monolayers demonstrate conductance modulation of more than five orders of magnitude. In addition, inverter circuits have been prepared that show a gain as high as six. The fabrication of monolayer transistors and inverters might represent an important step towards molecular-scale electronics.     

Measurement of the conductance of single conjugated molecules

Electrical conduction through molecules depends critically on the delocalization of the molecular electronic orbitals and their connection to the metallic contacts. Thiolated (- SH) conjugated organic molecules are therefore considered good candidates for molecular conductors: in such molecules, the orbitals are delocalized throughout the molecular backbone, with substantial weight on the sulphur-metal bonds. However, their relatively small size, typically approximately 1 nm, calls for innovative approaches to realize a functioning single-molecule device. Here we report an approach for contacting a single molecule, and use it to study the effect of localizing groups within a conjugated molecule on the electrical conduction. Our method is based on synthesizing a dimer structure, consisting of two colloidal gold particles connected by a dithiolated short organic molecule, and electrostatically trapping it between two metal electrodes. We study the electrical conduction through three short organic molecules: 4,4'-biphenyldithiol (BPD), a fully conjugated molecule; bis-(4-mercaptophenyl)-ether (BPE), in which the conjugation is broken at the centre by an oxygen atom; and 1,4-benzenedimethanethiol (BDMT), in which the conjugation is broken near the contacts by a methylene group. We find that the oxygen in BPE and the methylene groups in BDMT both suppress the electrical conduction relative to that in BPD.     

Real-time detection of electron tunnelling in a quantum dot

Nanostructures in which strong (Coulomb) interactions exist between electrons are predicted to exhibit temporal electronic correlations. Although there is ample experimental evidence that such correlations exist, electron dynamics in engineered nanostructures have been observed directly only on long timescales. The faster dynamics associated with electrical currents or charge fluctuations are usually inferred from direct (or quasi-direct) current measurements. Recently, interest in electron dynamics has risen, in part owing to the realization that additional information about electronic interactions can be found in the shot noise or higher statistical moments of a direct current. Furthermore, interest in quantum computation has stimulated investigation of quantum bit (qubit) readout techniques, which for many condensed-matter systems ultimately reduces to single-shot measurements of individual electronic charges. Here we report real-time observation of individual electron tunnelling events in a quantum dot using an integrated radio-frequency single-electron transistor. We use electron counting to measure directly the quantum dot's tunnelling rate and the occupational probabilities of its charge state. Our results provide evidence in favour of long (10 micros or more) inelastic scattering times in nearly isolated dots.     

双原子分子电子态振动跃迁F-C因子的计算

应用分立位置表象法(DPR)计算了双原子分子N2、Li2和CN在不同电子态之间发生振动跃迁的Franck-Condon因子,并用洛伦兹线型拟合了Li2分子低电子态振动跃迁的发射谱和吸收谱.结果表明,分立位置表象法是处理双原子分子振动问题的一种简单而有效的方法.DPR方法的计算程序可用于计算双原子分子的振动能级、波函数以及F-C因子.     

Indium phosphide nanowires as building blocks for nanoscale electronic and optoelectronic devices

Nanowires and nanotubes carry charge and excitons efficiently, and are therefore potentially ideal building blocks for nanoscale electronics and optoelectronics. Carbon nanotubes have already been exploited in devices such as field-effect and single-electron transistors, but the practical utility of nanotube components for building electronic circuits is limited, as it is not yet possible to selectively grow semiconducting or metallic nanotubes. Here we report the assembly of functional nanoscale devices from indium phosphide nanowires, the electrical properties of which are controlled by selective doping. Gate-voltage-dependent transport measurements demonstrate that the nanowires can be predictably synthesized as either n- or p-type. These doped nanowires function as nanoscale field-effect transistors, and can be assembled into crossed-wire p-n junctions that exhibit rectifying behaviour. Significantly, the p-n junctions emit light strongly and are perhaps the smallest light-emitting diodes that have yet been made. Finally, we show that electric-field-directed assembly can be used to create highly integrated device arrays from nanowire building blocks.     

Fabry - Perot interference in a nanotube electron waveguide

The behaviour of traditional electronic devices can be understood in terms of the classical diffusive motion of electrons. As the size of a device becomes comparable to the electron coherence length, however, quantum interference between electron waves becomes increasingly important, leading to dramatic changes in device properties. This classical-to-quantum transition in device behaviour suggests the possibility for nanometer-sized electronic elements that make use of quantum coherence. Molecular electronic devices are promising candidates for realizing such device elements because the electronic motion in molecules is inherently quantum mechanical and it can be modified by well defined chemistry. Here we describe an example of a coherent molecular electronic device whose behaviour is explicitly dependent on quantum interference between propagating electron waves-a Fabry-Perot electron resonator based on individual single-walled carbon nanotubes with near-perfect ohmic contacts to electrodes. In these devices, the nanotubes act as coherent electron waveguides, with the resonant cavity formed between the two nanotube-electrode interfaces. We use a theoretical model based on the multichannel Landauer-Büttiker formalism to analyse the device characteristics and find that coupling between the two propagating modes of the nanotubes caused by electron scattering at the nanotube-electrode interfaces is important.     

SO_2分子的532nm双光子激发及退激发过程

以纳秒Nd:YAG脉冲激光器的2倍频输出532nm激光作为激发源,采用双光子激发激光诱导色散荧光光谱方法对SO2分子第一激发带粒子的荧光辐射与碰撞弛豫相结合的复杂退激发过程进行了实验研究.结果表明,以215,337nm处荧光包络分别归属于C1B2,B1B1基振动能级到基电子态X1 A1不同振动能级的荧光跃迁,而425nm处荧光包络包既包含有a3B1基振动能级向基电子态X1 A1的荧光跃迁,同时还包含有C1B2基振动能级向A1 A2的荧光跃迁;由规则序列的实验数据可以计算出SO2分子相应电子态的对称振动和弯曲振动模式的基振动角频率及非谐性常数.所得结果对大气污染物SO2的探测及分子物理学研究具有重要意义.     

Electrical generation and absorption of phonons in carbon nanotubes

The interplay between discrete vibrational and electronic degrees of freedom directly influences the chemical and physical properties of molecular systems. This coupling is typically studied through optical methods such as fluorescence, absorption and Raman spectroscopy. Molecular electronic devices provide new opportunities for exploring vibration-electronic interactions at the single molecule level. For example, electrons injected from a scanning tunnelling microscope tip into a metal can excite vibrational excitations of a molecule situated in the gap between tip and metal. Here we show how current directly injected into a freely suspended individual single-wall carbon nanotube can be used to excite, detect and control a specific vibrational mode of the molecule. Electrons tunnelling inelastically into the nanotube cause a non-equilibrium occupation of the radial breathing mode, leading to both stimulated emission and absorption of phonons by successive electron tunnelling events. We exploit this effect to measure a phonon lifetime of the order of 10 ns, corresponding to a quality factor of well over 10,000 for this nanomechanical oscillator.