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.     

Molecular switching on surfaces

Molecular switching has established itself as a key functionality of building blocks developed for addressable materials and surfaces over the last two decades. Many challenges in their use and characterisation have been presented by the wide variation in interfaces studied, these ranging from truly single-molecule devices to two-dimensional self-assembled monolayers and thin films that bridge the gap between surface and macroscopically bulk materials (polymers, MOFs, COFs), and further still to other interfaces (solid–liquid, liquid–air, etc.). The low number density of molecules on monolayer-coated interfaces as well as in thin films, for example, presents substantial challenges in the characterisation of the composition of modified interfaces. The switching of molecular structure with external stimuli such as light and electrode potential adds a further layer of complexity in the characterisation of function. Such characterisation “in action” is necessary to correlate macroscopic phenomena with changes in molecular structure. In this review, key classes of molecular switches that have been applied frequently to interfaces will be discussed in the context of the techniques and approaches used for their operando characterisation. In particular, we will address issues surrounding the non-innocence of otherwise information-rich techniques and show how model – non-switching – compounds are often helpful in confirming and understanding the limitations and quirks of specific techniques.     

Photoswitchable double bonds: Synthetic strategies for tunability and versatility

Isomerizations of azo, imine, and alkene groups using light are highly tunable. As such, photoswitches based on these functional groups have become critical components of many responsive molecules and materials. This mini‐review describes recent work focused on controlling various properties of double bond‐based molecular switches, including speed of switching, thermal stability, and wavelength required to initiate switching. Methods used to control structure and function vary, but commonly involve careful probing of the electronic, photochemical, and steric profiles of the molecular switches. Successes and avenues for further investigation will be discussed.     

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.     

Surface photovoltage spectroscopy and thermally stimulated contact potential difference studies of real ZnS surfaces

Surface photovoltage spectroscopy and thermally stimulated contact potential difference measurements are reported for real ZnS surfaces. The measurements allow the determination of the surface states existing via two different processes, i.e. optical excitation of carriers into and from the existing surface states. Changing the surface condition by annealing at 350°C produces different electronic features which are attributed to different bondings at surface vacancy sites. Furthermore, annealing changes the polarity of the surface photovoltage.     

Excitation Properties of the Biological Neurons with Side-Inhibition Mechanism in Small-World Networks

We have studied the excitation properties of biophysical Hodgkin-Huxley neurons with the side-inhibition mechanism in small-world networks. The result shows that the excitation properties in the networks are preferably consistent with the characteristic properties of a brain neural system under external constant stimuli, such as fatigue effect, extreme excitation principle, and the brain neural excitation response induced by different in- tensity of noise and coupling. The results of the study might shed some light on the study of the brain nerve electrophysiology and epistemological science.     

Dynamics of optical and electrooptical switching in photo-thermal bistable CdS crystals

We investigate the dynamical properties of photo-thermal Self Electrooptic Effect Devices (SEEDs) fabricated of thin single crystal platelets in a wide region of excitation intensities at room temperature. Detailed characteristics of the switching processes and dynamics are precented for optical and for the first time for electro-optical types of bistable operation using an improved contact geometry. The role of the substrate of the SEED is also taken into account. It is shown that in the case of rectangular excitation pulses of light or of voltage the switching process can be divided into two regions, namely the crystal reaction time and the switching time itself. Both depend sensitively on the applied optical or electrical pulse height and also on the initial preheating. Critical slowing down is observed in the optical and the electrical case.Experimental results are discussed in terms of the thermal reaction of the crystal and of the substrate. The frequency dependencies of the switching processes are given. A quantitative theoretical analysis based on the heat conduction equation is done. Simple analytical formulas are deduced and discussed together with the experimental data.     

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.     

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.     

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.     

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     

Surface chemistry of hot electron and metal-oxide interfaces

Fundamental mechanisms for energy conversion and dissipation on surfaces and at interfaces have been significant issues in the community of surface science. Electronic excitation in exothermic chemical reactions or photon absorption involves the generation of energetic or hot electrons that are not in thermal equilibrium via non-adiabatic electronic excitation. A number of experimental and theoretical studies have demonstrated the influence of excited hot electrons on atomic and molecular processes, and it is a key moderator in the surface energy conversion process. The charge transfer through the metal-oxide interfaces has a significant impact on catalytic performance in mixed metal-oxide catalysts. In order to understand the influence of hot electrons and metal-oxide interfaces on the surface reactions, various detection schemes of exoelectron detection, including metal-insulator-metal and metal-semiconductor Schottky diodes, have been developed. Catalysts coupled with surface plasmons exhibit peculiar catalytic performance related to hot electron flow. In this review, we outline recent research efforts to relate hot electron flow with surface reactions occurring at metal-oxide interfaces. We report recent studies on the observation of hot electrons and the correlation between hot electrons and catalytic activity and selectivity on metallic surfaces. We show recent results from studies of surface reactions on nanocatalysts coupled with surface plasmons, where hot electron transport is the key process in energy dissipation and conversion processes.     

Evaluation of surface kinetic data by the transform analysis of modulated molecular beam measurements

The merits of different modulated molecular beam detection systems are discussed and the application of modern data handling methods described. It is shown that by using time domain analysis together with fourier transform techniques, information on the kinetics of surface processes is obtained. Data at a number of excitation frequencies is obtained in a single experiment. A means of detecting non-linear surface processes, and an accurate method for the determination of reaction orders is given. The origin of spurious coherent signals is considered, and finally the application of the techniques is illustrated with data obtained from an investigation of the interaction of modulated As₄ beams with GaAs surfaces.     

Total resonant absorption of light by plasmons on the nanoporous surface of a metal

We have calculated light absorption spectra of planar metal surfaces with a two-dimensional lattice of spherical nanovoids just beneath the surface. It is shown that nearly total absorption of light occurs at the plasma resonance in a void lattice in the visible range when the intervoid spacing and the void deepening into the metal are thinner than the skin depth, which ensures optimal coupling of void plasmons to external light. We conclude that the absorption and local-field properties of this type of nanoporous metal surface can be effectively tuned through nanoengineering of the spherical pores and that they constitute a very attractive system for various applications in future submicron light technology.     

Precessional switching of thin nanomagnets: analytical study

We study analytically the precessional switching of the magnetization of a thin macrospin. We analyze its response when subjected to an external field along its in-plane hard axis. We derive the exact trajectories of the magnetization. The switching versus non switching behavior is delimited by a bifurcation trajectory, for applied fields equal to half of the effective anisotropy field. A magnetization going through this bifurcation trajectory passes exactly along the hard axis and exhibits a vanishing characteristic frequency at that unstable point, which makes the trajectory noise sensitive. Attempting to approach the related minimal cost in applied field makes the magnetization final state unpredictable. We add finite damping in the model as a perturbative, energy dissipation factor. For a large applied field, the system switches several times back and forth. Several trajectories can be gone through before the system has dissipated enough energy to converge to one attracting equilibrium state. For some moderate fields, the system switches only once by a relaxation dominated precessional switching. We show that the associated switching field increases linearly with the damping parameter. The slope scales with the square root of the effective anisotropy. Our simple concluding expressions are useful to assess the potential application of precessional switching in magnetic random access memories.Received: 2 October 2003, Published online: 19 November 2003PACS: 75.40.Gb Dynamic properties (dynamic susceptibility, spin waves, spin diffusion, dynamic scaling, etc.) - 75.60.Jk Magnetization reversal mechanisms - 75.75. + a Magnetic properties of nanostructures     

One-way optoelectronic switching of photochromic molecules on gold

We investigate photochromic molecular switches that are self-assembled on gold. We use two experimental techniques; namely, the mechanically controllable break-junction technique to measure electronic transport, and UV/Vis spectroscopy to measure absorption. We observe switching of the molecules from the conducting to the insulating state when illuminated with visible light (lambda=546 nm), in spite of the gold surface plasmon absorption present around this wavelength. However, we fail to observe the reverse process which should occur upon illumination with UV light (lambda=313 nm). We attribute this to quenching of the excited state of the molecule in the open form by the presence of gold.     

Effects of input noise on a simple biochemical switch

Many biological processes are controlled by biomolecular switches which themselves are regulated by various upstream chemical molecules (the input). Understanding how input noise affects the output stochastic switching process is of significant interest in various biophysical systems like gene regulation, chemosensing, and cell motility. Here, we propose an exactly solvable model where the noisy input signal arises from a simple birth-death process and directly regulates the transition rates of a downstream switch. We solve the joint master equations to analyze the statistical properties of the output switching process. Our results suggest that the conventional wisdom of an additive input-output noise rule fails to describe signaling systems containing a single molecular switch, and, instead, the most important effect of input noise is to effectively reduce the on rate of the switch.