Electron beam irradiation for structuring of molecular assemblies

Nontraditional applications of electron beam irradiation for patterning of molecular assemblies are considered. The electron beam can have the following effects on molecular layers: destruction of molecular structure under e-beam irradiation with a successive formation of new molecular system when the irradiation is stopped; variation of the properties of the layer after e-beam irradiation; crosslinking of molecules in the layer under irradiation; modification of the templates for the successive film growth, providing different growing conditions in irradiated and nonirradiated areas; and activation of the solid support surface and molecular systems in the film resulting in the increased adhesion of the layer to the substrate in irradiated areas. All these effects were used for patterning of thin layers of different compounds. Five classes of molecular systems were considered, namely, films of simple surfactant molecules, layers of charge-transfer complexes, films of conducting polymers, aggregated nanoparticulate layers and films of nanoengineered polymeric capsules. Characteristic features of patterning processes in each particular case are discussed.     

Metal-free silicon-molecule-nanotube testbed and memory device

Work from several laboratories has shown that metal nanofilaments cause problems in some molecular electronics testbeds. A new testbed for exploring the electrical properties of single molecules has been developed to eliminate the possibility of metal nanofilament formation and to ensure that molecular effects are measured. This metal-free system uses single-crystal silicon and single-walled carbon nanotubes as electrodes for the molecular monolayer. A direct Si-arylcarbon grafting method is used. Use of this structure with pi-conjugated organic molecules resulted in a hysteresis loop with current-voltage measurements that are useful for an electronic memory device. The memory is non-volatile for more than 3 days, non-destructive for more than 1,000 reading operations and capable of more than 1,000 write-erase cycles before device breakdown. Devices without pi-conjugated molecules (Si-H surface only) or with long-chain alkyl-bearing molecules produced no hysteresis, indicating that the observed memory effect is molecularly relevant.     

Self-organized monolayer formation from binary mixtures of substituted alkyl chains studied by STM

The molecular assembly of p-iodo-phenyl octadecyl ether (I-POE), p-iodo-phenyl docosyl ether (I-PDE) and a binary mixture of these two molecules on graphite has been studied using a scanning tunneling microscope. Each molecular system self-assembles on the graphite surface to form a stable monolayer. For the binary system, the I-POE and I-PDE molecules do not mix on the surface, preferring instead to form isolated monolayer domains. Here, the I-POE molecules are preferentially adsorbed on the graphite surface, due to the effects of alkyl chain length and the functional group on the monolayer structure.     

Single-molecule devices: materials,structures and characteristics

This review article provides a brief survey of materials, structures and current state-of-the-art techniques used to measure the charge conduction characteristics of single molecules. Single molecules have been found to exhibit several unique functionalities including rectification, negative differential resistance and electrical bistable switching, all of which are necessary building blocks for the development and configuration of molecular devices into circuits. Conjugated organic molecules have received considerable interest for their low fabrication cost, three dimensional stacking and mechanical flexibility. Furthermore, the ability of molecules to self-assemble into well-defined structures is imperative for the fabrication of molecule based circuits. The theoretical formalisms are presented for studying single-molecule Coulomb blockade effects, ballistic transport in a molecular chain and electromagnetic coupling between a surface-plasmon field and a single molecule. Moreover, the experimental current–voltage results are discussed using basic principles of carrier transport mechanisms.     

Effects of hydration on molecular junction transport

The study of charge transport through increasingly complex small molecules will benefit from a detailed understanding of how contaminants from the environment affect molecular conduction. This should provide a clearer picture of the electronic characteristics of molecules by eliminating interference from adsorbed species. Here we use magnetically assembled microsphere junctions incorporating thiol monolayers to provide insight into changing electron transport characteristics resulting from exposure to air. Using this technique, current-voltage analysis and inelastic electron tunnelling spectroscopy (IETS) demonstrate that the primary interaction affecting molecular conduction is rapid hydration at the gold-sulphur contacts. We use IETS to present evidence for changing mechanisms of charge transport as a result of this interaction. The detrimental effects on molecular conduction discussed here are important for understanding electron transport through gold-thiol molecular junctions once exposed to atmospheric conditions.     

Strongly Correlated Aromatic Molecular Conductor

Strongly correlated electronic molecules open the way for strong coupling between charge, spin, and lattice degrees of freedom to enable interdisciplinary fields, such as molecular electronic switches and plasmonics, spintronics, information storage, and superconducting circuits. However, despite exciting computational predictions and promising advantages to prepare flexible geometries, the electron correlation effect in molecules has been elusive. Here, the electron correlation effects of molecular plasmonic films are reported to uncover their coupling of charge, spin, lattice, and orbital for the switchable metal‐to‐insulator transition under external stimuli, at which the simultaneous transition occurs from the paramagnetic, electrical, and thermal conducting state to the diamagnetic, electrical, and thermal insulating state. In addition, density functional theory calculation and spectroscopic studies are combined to provide the mechanistic understanding of electronic transitions and molecular plasmon resonance observed in molecular conducting films. The self‐assembled molecular correlated conductor paves the way for the next generation integrated micro/nanosystems.     

An ion-molecular chemical model of dense aluminum vapor plasma

A chemical model of nonideal gas-plasma mixture is proposed to describe a dense plasma of aluminum vapors. The molecules and the molecular ions are taken into consideration in addition to the conventionaly utilized set of electrons, ions and atoms to advance to low temperatures; doubly and triply ionized ions are considered for the high-temperature region. The effects of density are taken into account in a virial approximation. The virial corrections for the charge-charge and the charge-atom interactions are critically analyzed and chosen. The caloric and thermal equation of state, as well as the plasma composition have been obtained. It has been shown that an important role play molecules and molecular ions of aluminum especially in the early stage of heating of metal vapors. A satisfactory agreement with experimental results is obtained in the range of applicability of the model.     

Molecular Lubricants and Glues for Micro‐ and Nanodevices

Research advances in molecular coatings from functional polymeric and organic molecules designed as molecular lubricants or molecular glues for micro‐ and nanodevices are presented here, with a focus on organized molecular films from amphiphilic molecules, molecules with reactive ends and functional oligomers. The interfacial properties of molecular coatings critical for their lubrication (see Figure) or adhesive performance at the nanoscale are discussed in conjunction with results on molecular structure and morphology of these coatings. Examples of the latest developments in the field of nanocomposite molecular coatings and applications of molecular lubrication concepts for computer hard drives are presented.     

Modeling of transport phenomena of ions and polarizable molecules: A generalized Poisson–Nernst–Planck theory

A continuum theory of studying transport phenomena of ions and polarizable molecules in multi-component systems in the presence of electromagnetic fields is developed in this article. Physical effects of mass diffusion, heat conduction, mechanical motion, polarization and polarization relaxation in the mixture of the multi-component system, including their coupling effects, are formulated in accordance with the basic laws in non-equilibrium thermodynamics and continuum electrodynamics. A generalized Poisson–Nernst–Planck theory is introduced as a special case where thermo-mechanical effects are negligible. It is shown that electrodiffusion processes of mobile ions and polarizable molecules are generally coupled among diffusion fluxes as well as with the polarization of the molecules. For time-varying fields, the polarization relaxation of the molecules may also affect the electrodiffusion process. It is shown that the classical Poisson–Nernst–Planck theory can be recovered if these coupling effects are ignored in cases where such a simplification is justified. The generalized PNP theory formulated in the article may therefore offer a theoretical means to investigate the polarization–diffusion coupling effects of potential importance in the electrodiffusion processes of mobile ions and polarizable molecules at electrostatic cases as well as in time-varying fields, which could be of particular interest for revealing possible effects of exogenous time-varying fields on the ion transport properties and related functions of living cells. In general, the formulated theory may also be used to analyze some transport phenomena of nano-drug carriers in drug delivery systems as well as other molecular transport problems in engineering applications. While the theory is generally nonlinear, the linearization of the theory is possible in some cases. Illustratively, a coupled electrodiffusion wave problem is analyzed with a linearized model and its solution is discussed.     

Spin doping of individual molecules by using single-atom manipulation

Being able to control the spin of magnetic molecules at the single-molecule level will make it possible to develop new spin-based nanotechnologies. Gate-field effects and electron and photon excitations have been used to achieve spin switching in molecules. Here, we show that atomic doping of molecules can be used to change the molecular spin. Furthermore, a scanning tunneling microscope was used to place or remove the atomic dopant on the molecule, allowing us to change the molecular spin in a controlled way. Bis(phthalocyaninato)yttrium (YPc(2)) molecules deposited on an Au (111) surface keep their spin-1/2 magnetic moment due to the small molecule-substrate interaction. However, when Cs atoms were carefully placed onto YPc(2) molecules, the spin of the molecule vanished as shown by our conductance measurements and corroborated by the results of density functional theory calculations.     

Self‐Assembled Monolayer Transistors

Self‐assembled monolayers of organic, conjugated molecules can be used as active components of field‐effect transistors. The length of the molecule can define critical device dimensions with high precision on the nanometer scale. Transistor effects on the molecular‐scale as well as in devices consisting of single active molecules have been demonstrated. The observed device performance indicates that such transistors might be useful for switching and amplifying electrical signals in logic circuits. Moreover, functionalizing the organic molecules reveals that different parts of the molecule can act as gate insulator or the active component of transistors. Such research might pave the way to molecular electronic applications.     

Polyarene‐Functionalized Fullerenes in Carbon Nanotubes: Towards Controlled Geometry of Molecular Chains

Mechanisms for controlling the assembly of molecular arrays in carbon nanotubes via alteration of the size and geometry of the functional groups attached to the molecules inserted into the nanotubes are studied. As model compounds, a series of structurally related fullerenes functionalized with polyaryl groups (C₆₀X, where X is a polyaryl group) of various lengths are synthesized to explore this effect. These molecules are inserted into single‐walled carbon nanotubes (SWNTs) under mild conditions to prevent their decomposition and to form C₆₀X@SNWT structures. The molecular chains thus formed are studied by high‐resolution transmission electron microscopy, X‐ray diffraction, and Raman spectroscopy, revealing that the functional groups increase the interfullerene separation proportionally with the size of X. However, the functional groups themselves appear to adopt various orientations with respect to each other and exhibit intermolecular π–π interactions within the cavities of the carbon nanotubes. All these effects create a distribution of observed interfullerene separations in nanotubes, which are examined by theoretical simulations and interpreted in terms of molecular geometries and intermolecular interactions.     

Measurement of current-induced local heating in a single molecule junction

We have studied the current-induced local heating effects in single molecules covalently bound to two electrodes by measuring the force required to break the molecule-electrode bonds under various conditions. The breakdown process is thermally activated, which is used to extract the effective temperature of the molecular junction as a function of applied bias voltage. We have also performed first-principles calculations of both local heating and current-induced force effects, and the results are in good agreement with the experimental findings.     

Improved performance of nanocrystal quantum dots-based LEDs by modifying hole transport layer

Reported herein are the effects of the fabrication variables and surface capping of nanocrystal quantum dots (NQDs) on the characteristics of NQDs-based light-emitting diodes (LEDs). The molecular weight of the hole transport layer (HTL) material and the annealing conditions of the NQDs layer were chosen as fabrication process variables. Their effects on the layer characteristics and device efficiency were characterized. The maximum brightness varied over 50% according to the molecular weight of the HTL material. The optimized annealing temperature was shown to improve the maximum brightness by 20%. The surface-capping molecules of the NQDs were changed from conventional trioctyl phosphine/trioctyl phosphine oxide (TOPO/TOP) to pyridine and were incorporated into LEDs, and its effects on the device characteristics were discussed.     

Mechano-Chemical Interactions in the Use of Polyacrylic Acid as a Grinding Aid in Fine Grinding in Stirred Media Mills

ABSTRACT

Mechano-chemical interactions have been studied by using polyacrylic acid as a grinding aid for fine grinding in stirred media mills. The polymer additive was found to enhance grinding efficiency by up to 100%. Optimum operating conditions and mechanisms involved with the additive effects are discussed. It was also found that polymer conformation and polymer molecular weight change during stirred milling. Extension of the polymeric species and fragmentation of the high molecular weight polymer molecules resulting from grinding treatment may be beneficial.     

Field effects on the statistical behavior of the molecular conductance in a single molecular junction in aqueous solution

We have combined molecular dynamics simulations with first-principles calculations to study electron transport in a single molecular junction of perylene tetracarboxylic diimide (PTCDI) in aqueous solution under external electric gate fields. It is found that the statistics of the molecular conductance are very sensitive to the strength of the electric field. The statistics of the molecular conductance are strongly associated with the thermal fluctuation of the water molecules around the PTCDI molecule. Our simulations reproduce the experimentally observed three orders of magnitude enhancement of the conductance, as well as the temperature dependent conductance, under the electrochemical gates. The effects of the molecular polarization and the dipole rearrangement of the aqueous solution are also discussed.      

A metric for characterizing the bistability of molecular quantum-dot cellular automata

Much of molecular electronics involves trying to use molecules as (a)?wires, (b)?diodes or (c)?field-effect transistors. In each case the criterion for determining good performance is well known: for wires it is conductance, for diodes it is conductance asymmetry, while for transistors it is high transconductance. Candidate molecules can be screened in terms of these criteria by calculating molecular conductivity in forward and reverse directions, and in the presence of a gating field. Hence so much theoretical work has focused on understanding molecular conductance. In contrast a molecule used as a quantum-dot cellular automata (QCA) cell conducts no current at all. The keys to QCA functionality are (a)?charge localization, (b)?bistable charge switching within the cell and (c)?electric field coupling between one molecular cell and its neighbor. The combination of these effects can be examined using the cell-cell response function which relates the polarization of one cell to the induced polarization of a neighboring cell. The response function can be obtained by calculating the molecular electronic structure with ab initio quantum chemistry techniques. We present an analysis of molecular QCA performance that can be applied to any candidate molecule. From the full quantum chemistry, all-electron ab initio calculations we extract parameters for a reduced-state model which reproduces the cell-cell response function very well. Techniques from electron transfer theory are used to derive analytical models of the response function and can be employed on molecules too large for full ab initio treatment. A metric is derived which characterizes molecular QCA performance the way transconductance characterizes transistor performance. This metric can be assessed from absorption measurements of the electron transfer band or quantum chemistry calculations of appropriate sophistication.     

Vibration and orientation of diatomic molecules flowing through small carbon nanotubes

With their unique long cylindrical shape, carbon nanotubes may one-day form nozzles for nano-scale printing or flow into a chamber. Since the scale of the flowing molecules is similar to the diameter of the nanotubes, molecular vibration, orientation and density become influenced by the confinement during flow. We have studied the flow of diatomic molecules through carbon nanotube nozzles using non-equilibrium molecular dynamics simulations, in an effort to gain a greater understanding about the fundamental properties of such molecules in such a setting. The frequency of vibration of the molecules is shown to be dependent on the density inside the nanotubes and follow the same relation as an experimental micro-scale density-frequency study suggests, although only for nanotubes above a certain diameter. Meanwhile no relation is found between the frequency of vibration and the flow rate. The effect of nanotube diameter on the orientation of the molecules is also examined in detail, showing the transition between axial and radial orientation, with "pull" and "push" effects determining the orientation.     

Coherent collective precession of molecular rotors with chiral propellers

Successful attempts to manufacture synthetic molecular motors have recently been reported. However, compared with natural systems such as motor proteins, synthetic motors are smaller molecules and are therefore subject to thermal fluctuations that prevent them from performing any useful function. A mechanism is needed to amplify the single molecular motion to such a level that it becomes distinguishable from the thermal background. Condensation of molecular motors into soft ordered phases (such as liquid crystals) will be a feasible approach, because there is evidence that they support molecularly driven non-equilibrium motions. Here we show that a chiral liquid-crystalline monolayer spread on a glycerol surface acts as a condensed layer of molecular rotors, which undergo a coherent molecular precession driven by the transmembrane transfer of water molecules. Composed of simple rod-like molecules with chiral propellers, the monolayer exhibits a spatiotemporal pattern in molecular orientations that closely resembles 'target patterns' in Belousov-Zhabotinsky reactions. Inversion of either the molecular chirality or the transfer direction of water molecules reverses the rotation direction associated with switching from expanding to converging target patterns. Endowed only with the soft directional order, the liquid crystal is an optimal medium that helps molecular motors to manifest their individual motions collectively.     

有机分子电子器件的研究进展

随着传统硅基电子器件的发展日趋受限,以原子和分子作为电子元器件的研究受到了越来越多的重视.概述了分子电子器件的概念和基本原理,详细介绍了分子导线、分子二极管、分子开关、分子存储器件和分子场效应晶体管的工作原理及最近的研究进展.具有π-共轭结构的有机分子体系是构造分子导线的理想单元;分子结的电子结构不对称性是分子具有整流特性的根本原因;轮烷和索烃是构造分子开关的理想单元之一;分子场效应晶体管的工作原理是量子隧穿,主要是金属-绝缘体-金属间的隧穿效应.最后阐述了目前分子电子器件研究中存在的主要问题.