Optically and thermally induced molecular switching processes at metal surfaces

Using light to control the switching of functional properties of surface-bound species is an attractive strategy for the development of new technologies with possible applications in molecular electronics and functional surfaces and interfaces. Molecular switches are promising systems for such a route, since they possess the ability to undergo reversible changes between different molecular states and accordingly molecular properties by excitation with light or other external stimuli. In this review, recent experiments on photo- and thermally induced molecular switching processes at noble metal surfaces utilizing two-photon photoemission and surface vibrational spectroscopies are reported. The investigated molecular switches can either undergo a trans-cis?isomerization or a ring opening-closure reaction. Two approaches concerning the connection of the switches to the surface are applied: physisorbed switches, i.e.?molecules in direct contact with the substrate, and surface-decoupled switches incorporated in self-assembled monolayers. Elementary processes in molecular switches at surfaces, such as excitation mechanisms in photoisomerization and kinetic parameters for thermally driven reactions, which are essential for a microscopic understanding of molecular switching at surfaces, are presented. This in turn is needed for designing an appropriate adsorbate-substrate system with the desired switchable functionality controlled by external stimuli.     

Molecular switches at surfaces

In nature, molecules exploit interaction with their environment to realize complex functionalities on the nanometer length scale. Physical, chemical and/or biological specificity is frequently achieved by the switching of molecules between microscopically different states. Paradigmatic examples are the energy production in proton pumps of bacteria or the signal conversion in human vision, which rely on switching molecules between different configurations or conformations by external stimuli. The remarkable reproducibility and unparalleled fatigue resistance of these natural processes makes it highly desirable to emulate nature and develop artificial systems with molecular functionalities. A promising avenue towards this goal is to anchor the molecular switches at surfaces, offering new pathways to control their functional properties, to apply electrical contacts, or to integrate switches into larger systems. Anchoring at surfaces allows one to access the full range from individual molecular switches to self-assembled monolayers of well-defined geometry and to customize the coupling between molecules and substrate or between adsorbed molecules. Progress in this field requires both synthesis and preparation of appropriate molecular systems and control over suitable external stimuli, such as light, heat, or electrical currents. To optimize switching and generate function, it is essential to unravel the geometric structure, the electronic properties and the dynamic interactions of the molecular switches on surfaces. This special section, Molecular Switches at Surfaces, collects 17 contributions describing different aspects of this research field. They analyze elementary processes, both in single molecules and in ensembles of molecules, which involve molecular switching and concomitant changes of optical, electronic, or magnetic properties. Two topical reviews summarize the current status, including both challenges and achievements in the field of molecular switches on metal surfaces, focusing on electronic and vibrational spectroscopy in one case and scanning tunneling microscopy studies in the other. Original research articles describe results in many aspects of the field, including: Self-assembly, self-organization, and controlled growth of molecular layers on various substrates. Highly-ordered arrays provide model systems with extraordinary structural properties, allowing one to adjust interactions between molecules and between molecule and substrate, and can be robustly prepared from solution, an essential prerequisite for applications. Conformational or electronic switching of molecules adsorbed at metal and semiconductor surfaces. These studies highlight the elementary processes governing molecular switching at surfaces as well as the wide range of possible stimuli. Carbon-based substrates such as graphene or carbon nanotubes. These substrates are attractive due to their effective two-dimensionality which implies that switching of adsorbed molecules can effect a significant back-action on the substrate. Mechanisms of conformational switching. Several contributions study the role of electron-vibron coupling and heating in current-induced conformational switching. We hope that the collection of articles presented here will stimulate and encourage researchers in surface physics and interfacial chemistry to contribute to the still emerging field of molecular switches at surfaces. We wish to acknowledge the support and input from many colleagues in preparing this special section. A significant part of this work has been conducted in the framework of the Sonderforschungsbereich 658 Elementary Processes in Molecular Switches at Surfaces of the Deutsche Forschungsgemeinschaft, to which we are grateful for financial support. Molecular surfaces at switches contents Molecular switches at surfacesMartin Weinelt and Felix von Oppen Optically and thermally induced molecular switching processes at metal surfacesPetra Tegeder Effects of electron-vibration coupling in transport through single moleculesKatharina J Franke and Jose Ignacio Pascual Vibrational heating in single-molecule switches: an energy-dependent density-of-states approachT Brumme, R Gutierrez and G Cuniberti Reversible switching of single tin phthalocyanine molecules on the InAs(111)A surfaceC Nacci, K Kanisawa and S F?lsch Tuning the interaction between carbon nanotubes and dipole switches: the influence of the change of the nanotube-spiropyran distanceP Bluemmel, A Setaro, C Maity, S Hecht and S Reich Carbon nanotubes as substrates for molecular spiropyran-based switchesE Malic, A Setaro, P Bluemmel, Carlos F Sanz-Navarro, Pablo Ordejón, S Reich and A Knorr Ultrafast dynamics of dithienylethenes differently linked to the surface of TiO(2) nanoparticlesLars Dworak, Marc Zastrow, Gehad Zeyat, Karola Rück-Braun and Josef Wachtveitl Switching the electronic properties of Co-octaethylporphyrin molecules on oxygen-covered Ni films by NO adsorptionC F Hermanns, M Bernien, A Krüger, J Miguel and W Kuch STM-switching of organic molecules on semiconductor surfaces: an above threshold density matrix model for 1,5 cyclooctadiene on Si(100)K Zenichowski, Ch Nacci, S F?lsch, J Doki?, T Klamroth and P Saalfrank A switch based on self-assembled thymineFatih Kalkan, Michael Mehlhorn and Karina Morgenstern The growth and electronic structure of azobenzene-based functional molecules on layered crystalsJ Iwicki, E Ludwig, J Buck, M Kall?ne, F K?hler, R Herges, L Kipp and K Rossnagel Voltage-dependent conductance states of a single-molecule junctionY F Wang, N Néel, J Kr?ger, H Vázquez, M Brandbyge, B Wang and R Berndt Molecules with multiple switching units on a Au(111) surface: self-organization and single-molecule manipulationJohannes Mielke, Sofia Selvanathan, Maike Peters, Jutta Schwarz, Stefan Hecht and Leonhard Grill Preparing and regulating a bi-stable molecular switch by atomic manipulationS Sakulsermsuk, R E Palmer and P A Sloan Mixed self-assembled monolayers of azobenzene photoswitches with trifluoromethyl and cyano end groupsDaniel Brete, Daniel Przyrembel, Christian Eickhoff, Robert Carley, Wolfgang Freyer, Karsten Reuter, Cornelius Gahl and Martin Weinelt Reversible electron-induced cis-trans isomerization mediated by intermolecular interactionsCh Lotze, Y Luo, M Corso, K J Franke, R Haag and J I Pascual Transport properties of graphene functionalized with molecular switchesNiels Bode, Eros Mariani and Felix von Oppen.     

Light-driven molecular switches and motors

Technology is omnipresent in our modern-day society and it is hard to imagine a world without machines, computers or robots. One of the main current scientific challenges is the bottom-up construction of systems that represent nanosize analogues of switches, devices and motors. Our efforts in this area have focussed on the construction of devices based on sterically overcrowded alkenes. In this paper, we present our ongoing research on the construction of binary molecular switches, which has recently led to genuine molecular motors. The control of chirality in a molecular switching system allows interconversion between molecules of opposite helicity using different wavelengths of light. Such bistable chiral switches are of potential use in optical data storage and processing at the molecular level. The control of molecular chirality is even more subtle in the case of molecular motor systems. The exquisite control of chirality using light as an energy source has resulted in a controlled, repetitive 360° unidirectional rotation in two generations of molecular motor systems. Received: 21 January 2002 / Accepted: 11 February 2002 / Published online: 22 April 2002     

Optical Switching in Silicon Nanowaveguide Ring Resonators Based on Kerr Effect and TPA Effect

We analyze theoretically the 1 × 2 low-power all-optical switching in silicon nanowaveguide ring resonators （RR） based on the Kerr effect and two-photon absorption （TPA）, and give a comparison between both the all-optical switches. The calculation shows that the switching power of the TPA-RR switch is 3 orders smaller than that of the Kerr-RR switch. The switching time for both the switches is about 100ps.     

Au/MXene based ultrafast all-optical switching

All-optical switches have arisen great attention due to their ultrafast speed as compared with electric switches. However, the excellent optical properties and strong interaction of two-dimensional (2D) material MXene show great potentials in next-generation all-optical switching. As a solution, we propose all-optical switching used Au/MXene with switching full width at half maximum (FWHM) operating at 290 fs. Compared with pure MXene, the Au/MXene behaves outstanding performances due to local surface plasmon resonance (LSPR), including broadband differential transmission, strong near-infrared on/off ratio enhancement. Remarkably, this study enhances understanding of Au/MXene based ultrafast all-optical switching red-shifted about 34 nm in comparison to MXene, validating all optical properties of Au/MXene opening the way to the implementation of optical interconnection and optical switching.     

Coherence switching in a four-level system: quantum switching

Dark resonance switching among three-laser interactions in a four-level system is observed by using an enhanced nondegenerate four-wave mixing technique. This coherence switching mechanism is based on simultaneous suppression and enhancement of two-photon absorption and has a novel application to high-speed optical switches.     

Molecules with multiple switching units on a Au(111) surface: self-organization and single-molecule manipulation

Three different molecules, each containing two azobenzene switching units, were synthesized, successfully deposited onto a Au(111) surface by sublimation and studied by scanning tunneling microscopy at low temperatures. To investigate the influence of electronic coupling between the switching units as well as to the surface, the two azo moieties were connected either via π-conjugated para-phenylene or decoupling meta-phenylene bridges, and the number of tert-butyl groups was varied in the meta-phenylene-linked derivatives. Single molecules were found to be intact after deposition as identified by their characteristic appearance in STM images. Due to their mobility on the Au(111) surface at room temperature, the molecules spontaneously formed self-organized molecular arrangements that reflected their chemical structure. While lateral displacement of the molecules was accomplished by manipulation, trans-cis isomerization processes, typical for azobenzene switches, could not be induced.     

交叉波导中的非线性全光开关

提出了交叉波导结构中的非线性全光开关设想。用光束传输法，就自聚焦以及自散焦两种不同衬材料导，显示了全光开关的原理以及结构参量与开关特性之间的关系。     

Vibrational heating in single-molecule switches: an energy-dependent density-of-states approach

In recent experiments, it has been shown that the switching rate of single-molecule switches can show a rather complicated dependence on the applied bias voltage. Here, we discuss a minimal model which describes the switching process in terms of inelastic scattering processes of the tunneling electron by specific molecular vibrations. One important point is the introduction of an energy-dependent electronic density of states around the Fermi energy. The influence of different model parameters on the switching rate is studied and we show that the inclusion of a variable density of states allows us to understand the non-monotonic behavior of the switching rate observed in some experiments.     

Switching ability of nitro-spiropyran on Au(111): electronic structure changes as a sensitive probe during a ring-opening reaction

Spiropyran is a prototype molecular switch which undergoes a reversible ring-opening reaction by photoinduced cleavage of a C-O bond in the spiropyran (SP) to the merocyanine (MC) isomer. While the electronic states and switching behavior are well characterized in solution, adsorption on metal surfaces crucially affects these properties. Using two-photon photoemission and scanning tunneling spectroscopy, we resolve the molecular energy levels on a Au(111) surface of both isomeric forms. Illumination at various wavelengths does not yield any observable switching rate, thus evidencing a very small upper limit of the quantum efficiency. Electron-induced switching from the SP to the MC isomer via generation of a negative ion resonance can be detected with a quantum yield of (2.2 ± 0.2) × 10(-10) events/electron in tunneling spectroscopy. In contrast, the back reaction could not be observed. This study reveals that the switching properties of surface-bound molecular switches can be very different compared with free molecules, reflecting the strong influence of the interaction with the metal substrate.     

Fast high-voltage pulse generation using nonlinear capacitors

Many pulsed power applications require short high-voltage pulses with a high-repetition rate. Conventional high-voltage discharge pulse-switches such as thyratrons, spark gap switches, and vacuum tube switches have a short lifetime, whereas the semiconductor switches have a long lifetime and high reliability. The semiconductor switches, however cannot be directly applied to fast high-voltage pulsed power generation due to their limited operating voltage ratings despite their relatively long switching times. Therefore, they are used with voltage amplification and a pulse compression stage. This paper describes two pulse generators that use the semi-conductor switches and nonlinear capacitors: one is based on an opening switch (IGBT) and inductive energy storage, the other is a combination of a closing switch (RSD) and capacitive energy storage     

Adaptive synchronization of a switching system and its applications to secure communications

This paper studies the adaptive synchronization of a switching system with unknown parameters which switches between the R?ssler system and a unified chaotic system. Using the Lyapunov stability theory and adaptive control method, the receiver system will achieve synchronization with the drive system and the unknown parameters would be estimated by the receiver. Then the proposed switching system is used for secure communications based on the communication schemes including chaotic masking, chaotic modulation, and chaotic shift key strategies. Since the system switches between two chaotic systems and the parameters are almost unknown, it is more difficult for the intruder to extract the useful message from the transmission channel. In addition, two new schemes in which the chaotic signal used to mask (or modulate) the transmitted signal switches between two components of a chaotic system are also presented. Finally, some simulation results are given to show the effectiveness of the proposed communication schemes.     

Demonstration of a directed optical encoder using microring-resonator-based optical switches

We propose and demonstrate a directed optical logic circuit that performs the encoding function from a 4 bit electrical signal to a 2 bit optical signal based on cascaded microring switches. The four logic input signals control the states of the switches, while the two logic outputs are given by the optical power at the output waveguides. For proof of concept, a thermo-optic switching effect is used with an operation speed of 10 kbps.     

Fabrication of BDD quantum node switches on embedded GaAs quantum wires grown by selective MBE

In view of applications to hexagonal binary decision diagram (BDD) LSIs, a first attempt is made to form quantum BDD node switches on selectively grown (SG) embedded quantum wires (QWRs) by molecular beam epitaxy (MBE). SG branch switches controlled by a Schottky wrap gate (WPG) were successfully fabricated by MBE growth and subsequent device processing. Gate control characteristics were studied by gate-dependent Shubnikov–de-Haas measurements, and the behavior was found to be similar to that of devices fabricated on wires by etching. The switch exhibited clear conductance quantization at low temperature, and temperature dependence of the voltage slope of conductance jump was clarified. A Y-branch BDD node device using two SG branch switches was successfully fabricated, and realized clear path switching characteristics.     

Transport properties of graphene functionalized with molecular switches

We provide a theory of the electronic transport properties of a graphene layer functionalized with molecular switches. Our considerations are motivated by the spiropyran-merocyanine system which is non-polar in its ring-closed spiropyran form and zwitterionic in its ring-open merocyanine form. The reversible switching between these two isomers affects the carriers in graphene through the associated change in the molecular dipole moment, turning the graphene layer into a sensor of the molecular switching state. We present results for both the quasiclassical (Boltzmann) and the quantum coherent regimes of transport. Quite generally, we find a linear sensitivity of the conductance on the molecular dipole moment whenever quantum interference effects play an essential role which contrasts with a quadratic (and typically weaker) dependence when quantum interference is absent.     

Microscopic model of the optical absorption of carbon nanotubes functionalized with molecular spiropyran photoswitches

The adsorption of molecules to the surface of carbon nanostructures opens a new field of hybrid systems with distinct and controllable properties. We present a microscopic study of the optical absorption in carbon nanotubes functionalized with molecular spiropyran photoswitches. The switching process induces a change in the dipole moment leading to a significant coupling to the charge carriers in the nanotube. As a result, the absorption spectra of functionalized tubes reveal a considerable redshift of transition energies depending on the switching state of the spiropyran molecule. Our results suggest that carbon nanotubes are excellent substrates for the optical readout of spiropyran-based molecular switches. The gained insights can be applied to other noncovalently functionalized one-dimensional nanostructures in an externally induced dipole field.     

Fast optical switching via stimulated Raman adiabatic passage

We demonstrate a new approach to fast optical switching with a technique based on stimulated Raman adiabatic passage in which a laser pulse switches the probe field on and off via another coupling pulse. This new kind of optical switching is not limited by the decay rate of an excited state and can operate in the subnanosecond time domain. The experimental observation in Rb atomic vapor is in good agreement with numerical simulations.     

多模干涉马赫曾德尔光开关模型

根据N×N多模干涉耦合器的基本原理 ,确定了多模干涉耦合器的结构参数。通过分析多模干涉耦合器的输入光场与其映像间的相位关系 ,提出了模传输矩阵的分析方法 ,并用此方法分析了N×N普通干涉多模干涉耦合器、N×N相移器以及N×N普通干涉多模干涉马赫 曾德尔光开关 ,得到了它们的模场传输方程 ,分析了光开关在光场从任一输入端输入 ,从任一输出端输出时开关的驱动条件。用上面的方法分析了 4× 4光开关的结构及驱动条件     

Analysis of response characteristics for polymer directional coupler electro-optic switches

By using the coupled mode theory, electro-optic modulation theory, conformal transforming method, image method and the proposed transfer matrix technique, novel expressions for the both cases of the low switching frequency and the ultra-high switching frequency are presented for analyzing the transmission powers, rise time, fall time, switching time and switching frequency of the polymer directional coupler electro-optic switches. Simulation results of an application based on the technique show that, the switching voltage and coupling length are about 1.457 V and 4.374 mm, respectively, and the switching time and cutoff switching frequency are about 32.8 ps and 114.7 GHz, respectively, for the designed switch.