hand-controlled-manipulation-single-molecules-via-scanning-probe

Hand Controlled Manipulation of Single Molecules via a Scanning Probe Microscope with a 3D Virtual Reality Interface

Considering organic molecules as the functional building blocks of future nanoscale technology, the question of how to arrange and assemble such building ...

Forschungszentrum Jülich

Jülich Aachen Research Alliance (JARA)

The effect of molecular flexibility on the surface ordering of complex organic adsorbates is explored, using alpha,omega-dihexylquaterthiophene (DH4T) and mixed DH4T|tetracene phases on Ag(111) as model systems. The structure of DH4T/Ag(111) interfaces is determined by the flexibility of the hexyl chains at either end of the quaterthiophene backbone: Above 273 K, DH4T forms a nematic liquid crystalline phase with a director close to the [112] direction of the silver substrate. At 273 K, a reversible phase transition to a long-range ordered, point-on-line coincident phase is observed. However, this ordered state is still affected substantially by the flexible nature of DH4T, which materializes in a large number of local structural defects. If traces of DH4T are coevaporated with tetracene, inclusions of a 1:1 stoichiometric DH4T|tetracene phase are found in a tetracene/Ag(111) matrix (alpha-phase). In this mixed phase, the two surface enantiomers of pro-chiral DH4T on one hand and tetracene on the other form a complex stripe structure. The mixed phase shows a higher degree of order than present at the pure DH4T/Ag(111) interface, which also lacks chiral organization. The addition of tetracene molecules as structural templates stabilizes certain conformations of DH4T and thus, by balancing its structural flexibility, allows the surface-induced chirality of DH4T to become a decisive factor in determining the structure of the mixed phase.

Molecular flexibility as a factor affecting the surface ordering of organic adsorbates on metal substrates.

Local, noncovalent intermolecular interactions in organic monolayers have been directly imaged using scanning tunneling hydrogen microscopy (STHM). Unprecedented spatial resolution directly reveals the relation between the intermolecular interactions, the molecular chemical structure, and the ordering in the film.

Direct imaging of intermolecular bonds in scanning tunneling microscopy.

Individual Xe atoms as well as single CO and CH(4) molecules adsorbed at the tip apex of a scanning tunneling microscope (STM) function as microscopic force sensors that change the tunneling current in response to the forces acting from the surface. An STM equipped with any of these sensors is able to image the short-range Pauli repulsion and thus resolve the inner structure of large organic adsorbate molecules. Differences in the performance of the three studied sensors suggest that the sensor functionality can be tailored by tuning the interaction between the sensor particle and the STM tip.

Single molecule and single atom sensors for atomic resolution imaging of chemically complex surfaces.

The understanding and control of epitaxial growth of organic thin films is of crucial importance in order to optimize the performance of future electronic devices. In particular, the start of the submonolayer growth plays an important role since it often determines the structure of the first layer and subsequently of the entire molecular film. We have investigated the structure formation of 3,4,9,10-perylene-tetracarboxylic dianhydride and copper-phthalocyanine molecules on Au(111) using pair-potential calculations based on van der Waals and electrostatic intermolecular interactions. The results are compared with the fundamental lateral structures known from experiment and an excellent agreement was found for these weakly interacting systems. Furthermore, the calculations are even suitable for chemisorptive adsorption as demonstrated for copper-phthalocyanine/Cu(111), if the influence of charge transfer between substrate and molecules is known and the corresponding charge redistribution in the molecules can be estimated. The calculations are of general applicability for molecular adsorbate systems which are dominated by electrostatic and van der Waals interaction.

Modeling intermolecular interactions of physisorbed organic molecules using pair potential calculations.

We present evidence for a partly chemisorptive bonding between single monolayers of copper-II-phthalocyanine (CuPc) and 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) that are stacked on Ag(111). A commensurate registry between the two molecular layers and the substrate, i.e., a common crystallographic lattice for CuPc and PTCDA films as well as for the Ag(111) surface, indicates that the growth of the upper layer is dominated by the structure of the lower. Photoemission spectroscopy clearly reveals a gradual filling of the lowest unoccupied molecular orbital of PTCDA due to CuPc adsorption, which proves the chemisorptive character.

Commensurate registry and chemisorption at a hetero-organic interface.

The origin of the interface formation appearing due to the realization of contacts to ultrathin gold nanowire devices is revealed. Such interfaces play an important role in transport mechanisms in nanowire structures and can determine the electrical and operating parameters of a nanodevice. Based on experimental results, the specific electrical properties of bundles of ultrathin gold nanowires fabricated by wet chemical synthesis and subsequently assembled and contacted with gold electrodes are reported. It is demonstrated that these properties are strongly affected by the monolayers of organic molecules inevitably present on the surface of the nanowires due to synthetic conditions. In particular, such layers form a potential barrier to tunneling of the electrons from contacts to the nanowires. The electric transport behavior of the investigated nanowire structures in the temperature range from 500 mK to 300 K obeys the model of thermal fluctuation-induced tunneling conduction through the nanowire-metal electrode molecular junction. Application of this model allows calculation of the parameters of the molecular potential barrier. The formation of such a molecular barrier is verified by scanning tunneling microscope (STM) and transmission electron microscope (TEM) measurements performed using a supporting graphene layer. These findings are important for designing novel nanodevices for molecular electronics on the basis of ultrathin nanowires.

Features of transport in ultrathin gold nanowire structures.

Scanning probe microscopy (SPM) plays an important role in the investigation of molecular adsorption. The possibility to probe the molecule-surface interaction while tuning its strength through SPM tip-induced single-molecule manipulation has particularly promising potential to yield new insights. We recently reported experiments, in which 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) molecules were lifted with a qPlus-sensor and analyzed these experiments by using force-field simulations. Irrespective of the good agreement between the experiment and those simulations, systematic inconsistencies remained that we attribute to effects omitted from the initial model. Here we develop a more realistic simulation of single-molecule manipulation by non-contact AFM that includes the atomic surface corrugation, the tip elasticity, and the tip oscillation amplitude. In short, we simulate a full tip oscillation cycle at each step of the manipulation process and calculate the frequency shift by solving the equation of motion of the tip. The new model correctly reproduces previously unexplained key features of the experiment, and facilitates a better understanding of the mechanics of single-molecular junctions. Our simulations reveal that the surface corrugation adds a positive frequency shift to the measurement that generates an apparent repulsive force. Furthermore, we demonstrate that the scatter observed in the experimental data points is related to the sliding of the molecule across the surface.

The role of surface corrugation and tip oscillation in single-molecule manipulation with a non-contact atomic force microscope.

One of the paramount goals in nanotechnology is molecular-scale functional design, which includes arranging molecules into complex structures at will. The first steps towards this goal were made through the invention of the scanning probe microscope (SPM), which put single-atom and single-molecule manipulation into practice for the first time. Extending the controlled manipulation to larger molecules is expected to multiply the potential of engineered nanostructures. Here we report an enhancement of the SPM technique that makes the manipulation of large molecular adsorbates much more effective. By using a commercial motion tracking system, we couple the movements of an operator's hand to the sub-angstrom precise positioning of an SPM tip. Literally moving the tip by hand we write a nanoscale structure in a monolayer of large molecules, thereby showing that our method allows for the successful execution of complex manipulation protocols even when the potential energy surface that governs the interaction behaviour of the manipulated nanoscale object(s) is largely unknown.

Patterning a hydrogen-bonded molecular monolayer with a hand-controlled scanning probe microscope.

Van der Waals (vdW) forces act ubiquitously in condensed matter. Despite being weak on an atomic level, they substantially influence molecular and biological systems due to their long range and system-size scaling. The difficulty to isolate and measure vdW forces on a single-molecule level causes our present understanding to be strongly theory based. Here we show measurements of the attractive potential between differently sized organic molecules and a metal surface using an atomic force microscope. Our choice of molecules and the large molecule-surface separation cause this attraction to be purely of vdW type. The experiment allows testing the asymptotic vdW force law and its validity range. We find a superlinear growth of the vdW attraction with molecular size, originating from the increased deconfinement of electrons in the molecules. Because such non-additive vdW contributions are not accounted for in most first-principles or empirical calculations, we suggest further development in that direction.

Non-additivity of molecule-surface van der Waals potentials from force measurements.

Recently, the family of high-resolution scanning probe imaging techniques using decorated tips has been complemented by a method based on inelastic electron tunneling spectroscopy (IETS). The new technique resolves the inner structure of organic molecules by mapping the vibrational energy of a single carbon monoxide (CO) molecule positioned at the apex of a scanning tunneling microscope (STM) tip. Here, we explain high-resolution IETS imaging by extending a model developed earlier for STM and atomic force microscopy (AFM) imaging with decorated tips. In particular, we show that the tip decorated with CO acts as a nanoscale sensor that changes the energy of its frustrated translation mode in response to changes of the local curvature of the surface potential. In addition, we show that high resolution AFM, STM, and IETS-STM images can deliver information about the charge distribution within molecules deposited on a surface. To demonstrate this, we extend our mechanical model by taking into account electrostatic forces acting on the decorated tip in the surface Hartree potential.

Origin of High-Resolution IETS-STM Images of Organic Molecules with Functionalized Tips.

We introduce a scanning probe technique that enables three-dimensional imaging of local electrostatic potential fields with subnanometer resolution. Registering single electron charging events of a molecular quantum dot attached to the tip of an atomic force microscope operated at 5 K, equipped with a qPlus tuning fork, we image the quadrupole field of a single molecule. To demonstrate quantitative measurements, we investigate the dipole field of a single metal adatom adsorbed on a metal surface. We show that because of its high sensitivity the technique can probe electrostatic potentials at large distances from their sources, which should allow for the imaging of samples with increased surface roughness.

Scanning Quantum Dot Microscopy.

Controlled manipulation of single molecules is an important step towards the fabrication of single molecule devices and nanoscale molecular machines. Currently, scanning probe microscopy (SPM) is the only technique that facilitates direct imaging and manipulations of nanometer-sized molecular compounds on surfaces. The technique of hand-controlled manipulation (HCM) introduced recently in Beilstein J. Nanotechnol. 2014, 5, 1926-1932 simplifies the identification of successful manipulation protocols in situations when the interaction pattern of the manipulated molecule with its environment is not fully known. Here we present a further technical development that substantially improves the effectiveness of HCM. By adding Oculus Rift virtual reality goggles to our HCM set-up we provide the experimentalist with 3D visual feedback that displays the currently executed trajectory and the position of the SPM tip during manipulation in real time, while simultaneously plotting the experimentally measured frequency shift (Δf) of the non-contact atomic force microscope (NC-AFM) tuning fork sensor as well as the magnitude of the electric current (I) flowing between the tip and the surface. The advantages of the set-up are demonstrated by applying it to the model problem of the extraction of an individual PTCDA molecule from its hydrogen-bonded monolayer grown on Ag(111) surface.

Article	Year
Molecular flexibility as a factor affecting the surface ordering of organic adsorbates on metal substrates. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 17073481	2006
Direct imaging of intermolecular bonds in scanning tunneling microscopy. Journal of the American Chemical Society\| PubMed ID: 20698531	2010
Single molecule and single atom sensors for atomic resolution imaging of chemically complex surfaces. Journal of the American Chemical Society\| PubMed ID: 21962083	2011
Modeling intermolecular interactions of physisorbed organic molecules using pair potential calculations. The Journal of chemical physics\| PubMed ID: 22191896	2011
Commensurate registry and chemisorption at a hetero-organic interface. Physical review letters\| PubMed ID: 22463427	2012
Features of transport in ultrathin gold nanowire structures. Small (Weinheim an der Bergstrasse, Germany)\| PubMed ID: 23125023	2013
The role of surface corrugation and tip oscillation in single-molecule manipulation with a non-contact atomic force microscope. Beilstein journal of nanotechnology\| PubMed ID: 24605287	2014
Patterning a hydrogen-bonded molecular monolayer with a hand-controlled scanning probe microscope. Beilstein journal of nanotechnology\| PubMed ID: 25383304	2014
Non-additivity of molecule-surface van der Waals potentials from force measurements. Nature communications\| PubMed ID: 25424490	2014
Origin of High-Resolution IETS-STM Images of Organic Molecules with Functionalized Tips. Physical review letters\| PubMed ID: 25494078	2014
Scanning Quantum Dot Microscopy. Physical review letters\| PubMed ID: 26207484	2015
Virtual reality visual feedback for hand-controlled scanning probe microscopy manipulation of single molecules. Beilstein journal of nanotechnology\| PubMed ID: 26665087	2015

Ruslan Temirov

Biography

JoVE Journal Publications

Other Publications