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The formation of s-indaceno[1,2-b:5,6-b']ditetracene and as-indaceno[2,3-b:6,7-b']ditetracene containing indenofluorene cores from a common precursor has been achieved by a dehydrogenative surface-assisted cyclization on Au(111) and confirmed by bond-resolved non-contact atomic force microscopy. On-surface generated as-indaceno[2,3-b:6,7-b']ditetracenes undergo fusion, which leads to T-shaped adducts by an intermolecular cycloaddition. The same type of cycloaddition, which has no parallel in solution chemistry, has been observed between as-indaceno[2,3-b:6,7-b']ditetracene and pentacene or octacene. These examples of surface-assisted cycloaddition provide perspectives for the rational design and synthesis of molecular nanostructures.

Self-assembly of iron(II) phthalocyanine (FePc) molecules on a Ge(001):H surface results in monolayer islands extending over hundreds of nanometers and comprising upright-oriented entities. Scanning tunneling spectroscopy reveals a transport gap of 2.70 eV in agreement with other reports regarding isolated FePc molecules. Detailed analysis of single FePc molecules trapped at surface defects indicates that the molecules stay intact upon adsorption and can be manipulated away from surface defects onto a perfectly hydrogenated surface. This allows for their isolation from the germanium surface.

International audience; Surface-assisted synthesis has become a powerful approach for generation of molecular nanostructures, which could not be obtained via traditional solution chemistry. Nowadays there is an intensive search for reactions that could proceed on flat surfaces in order to boost the versatility and applicability of synthesized nano-objects. Here we propose application of atomic hydrogen combined with on-surface synthesis in order to tune the reaction pathways. We demonstrate that atomic hydrogen could be widely applied: (1) as a cleaning tool, which allows removal of halogen residues from the surface after Ullmann couplings/polymerization, (2) by reaction with surface organometallics to provide stable hydrogenated species, and (3) as a reagent for debromination or desulfurization of adsorbed species.

Nanographenes on oxides The growth of nanographene islands and ribbons on metal surfaces can be accomplished on single-crystal metal surfaces through carbon-carbon coupling reactions, but the surfaces of oxides do not assist these reactions. Kolmer et al. show that fluorinated aryl groups can be coupled to form nanographenes on the rutile surface of titanium oxide. The fluorine substitution of the aryl groups was selected so that as the carbon-fluorine bonds were thermally activated, a stepwise process sequentially added aromatic rings around a central aryl group until it was completely substituted. Science , this issue p. 57

A unified approach to the synthesis of the series of higher acenes up to previously unreported undecacene has been developed through the on‐surface dehydrogenation of partially saturated precursors. These molecules could be converted into the parent acenes by both atomic manipulation with the tip of a scanning tunneling and atomic force microscope (STM/AFM) as well as by on‐surface annealing. The structure of the generated acenes has been visualized by high‐resolution non‐contact AFM imaging and the evolution of the transport gap with the increase of the number of fused benzene rings has been determined on the basis of scanning tunneling spectroscopy (STS) measurements.

A nanographene formed by the fusion of 22 benzene rings has been prepared by combining an in-solution Pd-catalyzed cycloaddition reaction and on-surface Au-promoted cyclodehydrogenation. The structure and electronic properties of the resulting three-fold symmetric CH molecule have been characterized by scanning probe microscopy with atomic resolution and corroborated by theoretical modelling., This research was supported by the National Science Center, Poland (2017/26/E/ST3/00855), the EU project PAMS (610446), the Agencia Estatal de Investigacion (MAT2016-78293-C6-3-R, MAT2016-78293-C6-4-R, FIS2017-83780-P and CTQ2016-78157-R), the Xunta de Galicia (Centro singular de investigacion de Galicia, acreditacion 2016-2019, ED431G/09) and the European Regional Development Fund (ERDF). R. Z. acknowledges support received from the National Science Center, Poland (2017/24/T/ST5/00262).

Graphene nanoribbons (GNRs) and their derivatives attract growing attention due to their excellent electronic and magnetic properties as well as the fine-tuning of such properties that can be obtained by heteroatom substitution and/or edge morphology modification. Here, we introduce graphene nanoribbon derivatives—organometallic hybrids with gold atoms incorporated between the carbon skeleton and side Cl atoms. We show that narrow chlorinated 5-AGNROHs (armchair graphene nanoribbon organometallic hybrids) can be fabricated by on-surface polymerization with omission of the cyclodehydrogenation reaction by a proper choice of tailored molecular precursors. Finally, we describe a route to exchange chlorine atoms connected through gold atoms to the carbon skeleton by hydrogen atom treatment. This is achieved directly on the surface, resulting in perfect unsubstituted hydrogen-terminated GNRs. This will be beneficial in the molecule on-surface processing when the preparation of final unsubstituted hydrocarbon structure is desired., This work was supported by the National Science Center, Poland (2019/35/B/ST5/02666), and the EU Project PAMS (610446). A.G.L., D.S.P., and P.B. acknowledge the Spanish Agencia Estatal de Investigación (Grants MAT2016-78293-C6-4-R, PID2019-107338RB-C66, and FIS2017-83780-P), Dep. Educación of the Basque Government and UPV/EHU (Grant IT-756-13), and the European Union (EU) through Horizon 2020 (FET-Open project SPRING Grant 863098) for support.

Miniaturization of electronic circuits into the single-atom level requires novel approaches to characterize transport properties. Due to its unrivaled precision, scanning probe microscopy is regarded as the method of choice for local characterization of atoms and single molecules supported on surfaces. Here we investigate electronic transport along the anisotropic germanium (001) surface with the use of two-probe scanning tunneling spectroscopy and first-principles transport calculations. We introduce a method for the determination of the transconductance in our two-probe experimental setup and demonstrate how it captures energy-resolved information about electronic transport through the unoccupied surface states. The sequential opening of two transport channels within the quasi-one-dimensional Ge dimer rows in the surface gives rise to two distinct resonances in the transconductance spectroscopic signal, consistent with phase-coherence lengths of up to 50 nm and anisotropic electron propagation. Our work paves the way for the electronic transport characterization of quantum circuits engineered on surfaces., This work was supported by the FP7 FET-ICT “Planar Atomic and Molecular Scale devices” (PAMS) project (funded by the European Commission under contract number 610446), the Polish Ministry for Science and Higher Education from financial resources for science in 2013–2017 granted for an international co-financed project (contract number 2913/7.PR/2013/2) and the Spanish Ministerio de Economía y Competitividad (MINECO) (Grant Numbers MAT2016-78293-C6-4-R and FIS2017-83780-P). M.K. acknowledges financial support received from the Polish Ministry of Science and Higher Education, contract number 0341/IP3/2016/74.

Synthesis of a triporous nanographene with 102 sp2 carbon atoms by combining solution and surface chemistry., The synthesis of porous nanographenes is a challenging task for solution chemistry, and thus, on-surface synthesis provides an alternative approach. Here, we report the synthesis of a triporous nanographene with 102 sp2 carbon atoms by combining solution and surface chemistry. The carbon skeleton was obtained by Pd-catalyzed cyclotrimerization of arynes in solution, while planarization of the molecule was achieved through two hierarchically organized on-surface cyclodehydrogenation reactions, intra- and inter-blade. Remarkably, the three non-planar [14]annulene pores of this nanographene further evolved at higher temperatures showing interesting intra-porous on-surface reactivity.

Understanding the mechanisms involved in the covalent attachment of organic molecules to surfaces is a major challenge for nanotechnology and surface science. On the basis of classical organic chemistry mechanistic considerations, key issues such as selectivity and reactivity of the organic adsorbates could be rationalized and exploited for the design of molecular-scale circuits and devices. Here we use tris(benzocyclobutadieno)triphenylene, a singular Y-shaped hydrocarbon containing antiaromatic cyclobutadienoid rings, as a molecular probe to study the reaction of polycyclic conjugated molecules with atomic scale moieties, dangling-bond (DB) dimers on a hydrogen-passivated Ge(001):H surface. By combining molecular design, synthesis, scanning tunneling microscopy and spectroscopy (STM/STS) and computational modeling, we show that the attachment involves a concerted [4+2] cycloaddition reaction that is completely site-selective and fully reversible. This selectivity, governed by the bond alternation induced by the presence of the cyclobutadienoid rings, allows for the control of the orientation of the molecules with respect to the surface DB-patterning. We also demonstrate that by judicious modification of the electronic levels of the polycyclic benzenoid through substituents, the reaction barrier height can be modified. Finally, we show that after deliberate tip-induced covalent bond cleavage, adsorbed molecules can be used to fine tune the electronic states of the DB dimer. This power to engineer deliberately the bonding configuration and electronic properties opens new perspectives for creating prototypical nanoscale circuitry., This work was supported by the FP7 FET-ICT “Planar Atomic and Molecular Scale devices” (PAMS) project (funded by the European Commission under contract no. 610446), by the Polish Ministry for Science and Higher Education from financial resources for science in 2013–2017 granted for an international co-financed project (contract no. 2913/7.PR/2013/2) and by projects CTQ2016-78157-R, MAT2016-78293-C6-3R and MAT2016-78293-C6-4R (AEI/FEDER, UE). EG, DP and DP are grateful for financial support from the Xunta de Galicia (Centro singular de investigación de Galicia accreditation 2016–2019, ED431G/09) and the European Union (European Regional Development Fund-ERDF).

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence., Dangling bond (DB) arrays on Si(001):H and Ge(001):H surfaces can be patterned with atomic precision and they exhibit complex and rich physics making them interesting from both technological and fundamental perspectives. But their complex behavior often makes scanning tunneling microscopy (STM) images difficult to interpret and simulate. Recently it was shown that low-temperature imaging of unoccupied states of an unpassivated dimer on Ge(001):H results in a symmetric butterfly-like STM pattern, despite that the equilibrium dimer configuration is expected to be a bistable, buckled geometry. Here, based on a thorough characterization of the low-bias switching events, we propose a new imaging model featuring a dynamical two-state rate equation. This model allows us to reproduce the features of the observed symmetric empty-state images which strongly corroborates the idea that the patterns arise due to fast switching events and provides insight into the relation between the tunneling current and switching rates. Our new imaging model is general and can be applied to other systems that exhibit rapid fluctuations during STM experiments., The work is funded by the European Commission under the FP7 FET-ICT “Planar Atomic and Molecular Scale devices” (PAMS) project (Contract No. 610446) and National Science Centre, Poland (2014/15/D/ST3/02975). ME, TF, and DSP also acknowledge support from the Spanish Ministerio de Economía y Competitividad (MINECO) (Grant No. MAT2013-46593-C6-2-P) and the Basque Dep. de Educación and the UPV/EHU (Grant No. IT-756-13). MK acknowledges financial support received from the Foundation for Polish Science (FNP). RZ acknowledges support received from KNOW (scholarship KNOW/44/SS/RZ/2015)., We acknowledge support by the CSIC Open Access Publication Initiative through its Unit of Information Resources for Research (URICI).

Transformations of molecular structures formed by perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecules on a rutile TiO2(110) surface are studied with low-temperature scanning tunnelling microscopy. We demonstrate that metastable molecular assemblies transform into differently ordered structures either due to additional energy provided by thermal annealing or when the influence of intermolecular forces is increased by the enlarged amount of deposited molecules. Proper adjustment of molecular coverage and substrate temperature during deposition allows for fabrication of desired assemblies. Differences between PTCDA/TiO2(110) and PTCDA/TiO2(011) systems obtained through identical experimental procedures are discussed.

cited By 18; International audience; Fabrication of single-molecule logic devices requires controlled manipulation of molecular states with atomic-scale precision. Tuning molecule–substrate coupling is achieved here by the reversible attachment of a prototypical planar conjugated organic molecule to dangling bonds on the surface of a hydrogenated semiconductor. We show that the ground electronic state resonance of a Y-shaped polyaromatic molecule physisorbed on a defect-free area of a fully hydrogenated surface cannot be observed by scanning tunneling microscopy (STM) measurements because it is decoupled from the Ge bulk states by the hydrogen-passivated surface. The state can be accessed by STM only if the molecule is contacted with the substrate by a dangling bond dimer. The reversibility of the attachment processes will be advantageous in the construction of surface atomic-scale circuits composed of single-molecule devices interconnected by the surface dangling bond wires.

Graphical abstractDisplay Omitted HighlightsWe prepare and characterize fully passivated Ge(001)-(2i?1):H surface.We describe a protocol for dimer-by-dimer STM tip-induced hydrogen desorption.Atomically precise dangling bond (DB) logic gate is successfully constructed.Feasibility of DB logic gate implementation on hydrogenated Ge is demonstrated. We describe a complete protocol for atomically precise dangling bond (DB) logic gate construction on a hydrogenated Ge(001):H surface. Starting from the preparation of the reconstructed Ge(001) surface followed by its passivation with hydrogen atoms we end up with the platform for scanning tunneling microscopy (STM) atomic-scale lithography. Finally with the use of dimer-by-dimer STM tip-induced hydrogen desorption from the Ge(001)-(2i?1):H surface the DB nanostructures of pre-designed form are fabricated. Furthermore, the STM tip manipulation provides the control over the buckling phase of a single DB dimer incorporated into the DB logic gate structure, which is of crucial importance for the final electronic properties of the system. Our results prove feasibility of DB atomic scale logic gate implementation on the passivated semiconductor surfaces.

To explore the origin of the Fermi level pinning in germanium we investigate the Ge(001) and Ge(001):H surfaces. The absence of relevant surface states in the case of Ge(001):H should unpin the surface Fermi level. This is not observed. For samples with donors as majority dopants the surface Fermi level appears close to the top of the valence band regardless of the surface structure. Surprisingly, for the passivated surface it is located below the top of the valence band allowing scanning tunneling microscopy imaging within the band gap. We argue that the well known electronic mechanism behind band bending does not apply and a more complicated scenario involving ionic degrees of freedom is therefore necessary. Experimental techniques involve four point probe electric current measurements, scanning tunneling microscopy and spectroscopy., Comment: 5 pages, 4 figures

This work is licensed under a Creative Commons Attribution 4.0 International License., We present a combined experimental and theoretical study of the electronic properties of close-spaced dangling-bond (DB) pairs in a hydrogen-passivated Si(001):H p-doped surface. Two types of DB pairs are considered, called >cross> and >line> structures. Our scanning tunneling spectroscopy (STS) data show that, although the spectra taken over different DBs in each pair exhibit a remarkable resemblance, they appear shifted by a constant energy that depends on the DB-pair type. This spontaneous asymmetry persists after repeated STS measurements. By comparison with density functional theory (DFT) calculations, we demonstrate that the magnitude of this shift and the relative position of the STS peaks can be explained by distinct charge states for each DB in the pair. We also explain how the charge state is modified by the presence of the scanning tunneling microscopy (STM) tip and the applied bias. Our results indicate that, using the STM tip, it is possible to control the charge state of individual DBs in complex structures, even if they are in close proximity. This observation might have important consequences for the design of electronic circuits and logic gates based on DBs in passivated silicon surfaces., This work is funded by the FP7 FET-ICT “Planar Atomic and Molecular Scale devices” (PAMS) project (funded by the European Commission under contract No. 610446). ME, TF, AGL and DSP also acknowledge support from the Spanish Ministerio de Economía y Competitividad (MINECO) (Grant No. MAT2013-46593-C6-2-P) and the Basque Dep. de Educación and the UPV/EHU (Grant No. IT-756-13). MK acknowledges financial support received from the Polish National Science Centre for preparation of his PhD dissertation (decision number: DEC-2013/08/T/ST3/00047) and from the Foundation for Polish Science (FNP).

We show that a dangling bond (DB) dimer on Ge(001):H exhibits a dynamical behavior when the empty states are imaged with scanning tunneling microscopy (STM) at liquid helium temperature. Large amplitude Ge atom vibrations are decisive in facilitating a specific appearance of the structure in the STM images. The underlying mechanism is unraveled using a theoretical model and calculations within the density functional theory framework. Furthermore, we demonstrate the ability to induce controlled switching of the DB dimer with noncontact atomic force microscope and the stabilizing role of the dimer-dimer interaction.

The structure of a hydrogenated Ge(001) surface is examined by means of non-contact atomic force microscopy (NC-AFM) at 5 K. Three-dimensional force spectroscopy of a bond defect surrounded by a passivated area shows a qualitatively distinct spatial dependence of the interaction. The force curve over a defect has a range where the short-range attractive force is detected, whereas over the hydrogen-terminated bonds, it is missing: atomic-scale imaging of hydrogens is possible only in the repulsive range. Thus, NC-AFM allows for clear determination of the different chemical activities of the defect compared to the surrounding passivated area.

cited By 21; International audience; Specific surfaces allowing the ultra-high vacuum (UHV) creation of electronic interconnects and atomic nanostructures are required for the successful development of novel nanoscale electronic devices. Atomically flat and reconstructed Si(0 0 1):H surfaces are serious candidates for that role. In this work such Si:H surfaces were prepared in a cleanroom environment on 200 mm silicon wafers with a hydrogen bake and were subsequently bonded together to ensure the surface protection, and allow their transportation and storage for several months in air. Given the nature of the bonding, which was hydrophobic with weak van der Waals forces, we were then able to de-bond them in UHV. We show that the quality of the de-bonded Si:H surface enables the “at will” construction of sophisticated and complex dangling bond (DB) nanostructures by atomically precise scanning tunneling microscope (STM) tip induced desorption of hydrogen atoms. The DB structures created on slightly doped Si:H samples were characterized by scanning tunneling microscopy and spectroscopy (STM/STS) performed at 4 K. Our results demonstrate that DB nanostructures fabricated on UHV de-bonded Si(0 0 1):H wafers could be directly incorporated in future electronics as interconnects and parts of nanoscale logic circuits.

On-surface polymerization is feasible on semiconducting surfaces. Thermally triggered covalent coupling of 10,10′-dibromo-9,9′-bianthryl molecules on the TiO2(011)-(2×1) surface is demonstrated. The result paves the way for application of the thermally driven on-surface polymerization on semiconducting surfaces and indicates that methods based on such a reaction are more universal than previously thought.

We report on studies concerning individual trinaphthylene molecules (Y molecules) deposited and anchored on the hydrogenated Ge(001):H surface. The characterization of single Y molecules has been performed by means of cryogenic temperature STM imaging using conventional STM tungsten tips and tuning fork-based sensors. In the latter case, a qPlus sensor facilitated simultaneous STM and NC-AFM measurements and thus molecular states were probed by both tunneling current and atomic forces concurrently. We show that the molecules are physisorbed, thus weakly interacting with the substrate. Contrary to the measurements on hydrogenated silicon, for planar aromatic molecules on the hydrogenated germanium, both empty and filled molecular states could be probed by STM.

Atomically precise dangling-bond (DB) lines are constructed dimer-by-dimer on a hydrogen-passivated Ge(001)-(2$\ifmmode\times\else\texttimes\fi{}$1):H surface by an efficient scanning tunneling microscope (STM) tip-induced desorption protocol. Due to the smaller surface band gap of the undoped Ge(001) substrate compared to Si(001), states associated with individually created DBs can be characterized spectroscopically by scanning tunneling spectroscopy (STS). Corresponding $dI/dV$ spectra corroborated by first-principle modeling demonstrate that DB dimers introduce states below the Ge(001):H surface conduction band edge. For a DB line parallel to the surface reconstruction rows, the DB-derived states near the conduction band edge shift to lower energies with increasing number of DBs. The coupling between the DB states results in a dispersive band spanning 0.7 eV for an infinite DB line. For a long DB line perpendicular to the surface reconstruction rows, a similar band is not formed since the interdimer coupling is weak. However, for a short DB line (2--3 DBs) perpendicular to the reconstruction rows a significant shift is still observed due to the more flexible dimer buckling.

Adsorption and self-assembly of large π-conjugated 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) molecules on rutile TiO(2)(110) surface have been investigated using a combination of high-resolution scanning tunneling microscopy (STM), low-energy electron diffraction, and density functional theory calculations with inclusion of Grimme treatment of the dispersion forces (DFT-D). Evolution of the STM images as a function of PTCDA coverage is caused by transition of the adsorption mode from physisorbed single adspecies and meandering stripes into spontaneously ordered chemisorbed molecular assemblies. This change in the adsorption fashion is accompanied by significant bending of the intrinsically flat, yet elastic, PTCDA molecule, which allows for strong electronic coupling of the dye adspecies with the TiO(2) substrate. Extensive DFT-D modeling has revealed that adsorption is controlled by interfacial and intermolecular dispersion forces playing a dominant role in the adsorption of single PTCDA species, their self-organization into the meandering stripes, and at the monolayer coverage acting collectively to surmount the chemisorption energy barrier associated with the molecule bending. Analysis of the resulting density of states has revealed that alignment of the energy levels and strong electronic coupling at the PTCDA/TiO(2) interface are beneficial for dye sensitization purposes.

Helicenes are carbon-rich materials with an ordered structure that possess interesting and remarkable electronic, chiroptical, mechanical and magnetic properties either in bulk or as single molecule devices. We report on the first attempt to anchor and organize {[}11]anthrahelicene ({[}11]AH) molecules onto a metal oxide surface. Molecular structures obtained on the (110) and (011) faces of rutile titania are characterized using scanning probe microscopy. On the (110) surface, {[}11]AH molecules form islands that are comprised of small domains of two types that are mirror reflections of each other and have an ordered quasi-hexagonal lattice. In contrast, molecules form unordered clusters on the (011) surface. Single molecules on both faces are imaged with sub-molecular resolution. (C) 2012 Elsevier B.V. All rights reserved

The demand to discover new, alternative solutions in future electronics has currently focused the attention on the possible use of single atomic wires and conductive mesa pads as components in electronic circuits. For such applications, we need a good knowledge of structural and electronic properties of 1D and 2D conductive nanostructures fabricated on large and/or moderate band gap semiconductor surfaces. This chapter is reporting on case studies invoking preparation of well organized atomic wires and 2D conductive pads by self-assembly of gold atoms on clean, reconstructed Ge(001) surface. Structural characterization of the fabricated nanostructures was performed with atomic resolution on low temperature scanning tunneling microscope (LT-STM) and multi-probe STM designed by Omicron Nanotechnology GmbH. Using the far field, high resolution scanning electron microscope (SEM), the pre-prepared nanostructures were identified after an UHV transfer into a multi-probe station of the system, and their surface conductance was measured with two STM probes. The conductance dependence as a function of the inter-probe distance confirmed 2D (surface) character of the Au rich nanostructures assembled on Ge(001).

The self-assembling of 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) molecules deposited on an InSb(001) c(8 $\times$ 2) surface at sub-monolayer quantities has been investigated at low temperature (77 K) using scanning tunnelling microscopy. Sub-molecular resolution was obtained on PTCDA molecules. The results reveal that individual PTCDA molecules are arranged on the substrate in chains parallel to the [110] crystallographic direction, correlated with characteristic features of the low temperature InSb(001) c(8 $\times$ 2) surface electronic structure. A structural model for PTCDA molecules adsorbed on InSb is proposed.

An extensive scanning tunneling microscopy (STM) study of adsorption of submonolayer coverages of PTCDA molecules on the $c(8\ifmmode\times\else\texttimes\fi{}2)$ reconstructed InSb(001) surface is presented together with ab initio density functional theory (DFT) calculations. Our DFT calculations explain the variety of adsorption sites seen on the experimental STM images. In particular, we prove that the molecules are oriented with their long axes along the [110] direction. Calculated STM images of the molecule agree well with the high-resolution STM images obtained at the temperature of 77 K. We find that molecules form four covalent bonds between edge oxygen atoms of the PTCDA and In atoms of the surface. We also study in detail their diffusion mechanism and explain their ability to form experimentally observed chains along the [110] direction.

In this report we present results of combined high resolution LT-STM and LEED studies of ultrathin epitaxial KBr films grown on an InSb(0 0 1) c(8 × 2) substrate. Based on atomically resolved STM maps and LEED diffractograms the film structure as well as superimposed electronic effects are explained. The origin of additional 4 × 4 superstructure observed on ultrathin films is discussed. Possible application of the KBr/InSb system as a template for growing organic molecule structures is suggested.

Self-organization of 1,4-benzenedicarboxylic acid molecules (terephthalic acid, TPA) on a rutile TiO2(110)-(1×1) surface is studied by means of ultra-high vacuum scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM). When saturation coverage is achieved with the formation of one monolayer, STM images reveal two alternating contrast patterns: (i) a well-organized (2×1) structure and (ii) a mixed structure of molecular rows oriented along the 001 crystallographic direction. Complementary STM images recorded with two different tip terminations prove that the two contrasting patterns indicate the same stable surface structure. The nc-AFM imaging confirms the mixed molecular row structure. It is concluded that TPA molecules are adsorbed in an upright position. This occurs with one of the carboxyl group bound dissociatively in a bi-dentate fashion with the two 5-fold coordinated Ti atoms. The second carboxyl group is exposed to the vacuum interface. This carboxyl terminated surface is discussed in terms of surface chemical functionalization.

High resolution scanning tunneling microscopy has been applied to investigate adsorption and self-assembly of large organic molecules on the TiO(2)(011) surface. The (011) face of the rutile titania has been rarely examined in this context. With respect to possible industrial applications of rutile, quite often in a powder form, knowledge on behavior of organic molecules on that face is required. In the presented study we fill in the gap and report on experiments focused on the self-assembly of organic nanostructures on the TiO(2)(011) surface. We use three different kinds of organic molecules of potential interest in various applications, namely, PTCDA and CuPc representing flat, planar stacking species, and Violet Landers specially designed for new applications in molecular electronics. In order to reach a complete picture of molecular behavior, extended studies with different surface coverage ranging from single molecule up to 2 monolayer (ML) thick films are performed. Our results show that the adsorption behavior is significantly different from previously observed for widely used metallic templates. Creation of highly ordered molecular lines, quasi-ordered wetting layers, controlled geometrical reorientation upon thermal treatment, existence of specific adsorption geometries, and prospects for tip-induced molecule ordering and manipulation provide better understanding and add new phenomena to the knowledge on the (011) face of rutile titania.

The adsorption of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) on a rutile TiO(2)(011)-(2 × 1) surface is studied using ultra-high vacuum scanning tunneling microscopy. The self-assembly process is dominated by the fine interplay between the lateral intermolecular interactions and the binding to the substrate. By means of temperature-induced change in the adsorption configuration and the activation of diffusion, the molecules are assembled into one-dimensional chains oriented along the [Formula: see text] crystallographic direction.

We have used scanning tunnelling microscopy (STM) at 77 K to investigate 3,4,9,10-perylene-tetracarboxylic dianhydride (PTCDA) molecules adsorbed on an ultrathin (1–2 monolayer (ML)) film of KBr grown on a c(8 $\times$ 2)InSb(001) substrate. The molecules are stabilized both at the KBr steps and on the terraces. On the 1 ML film the PTCDA molecules appear predominantly as single entities, whereas on the 2 ML film formation of molecular clusters is preferred. Differences in the adsorption configurations indicate that the interaction between the molecules and the surface differs significantly for the cases of 1 and 2 ML films. We present images of the molecules obtained with sub-molecular resolution for both filled and empty state sampling modes. We argue that the highest occupied molecular orbital (the lowest unoccupied molecular orbital) is responsible for intramolecular contrast in filled (empty) state images of the molecules, even though they are deformed due to strong interaction with the substrate.

Molecular heterostructures are formed from meso-tetraphenyl porphyrins-Zn(II) (ZnTPP) and Cu(II)-phthalocyanines (CuPc) on the rutile TiO2(011) surface. We demonstrate that ZnTPP molecules form a quasi-ordered wetting layer with flat-lying molecules, which provides the support for growth of islands comprised of upright CuPc molecules. The incorporation of the ZnTPP layer and the growth of heterostructures increase the stability of the system and allow for room temperature scanning tunneling microscopy (STM) measurements, which is contrasted with unstable STM probing of only CuPc species on TiO2. We demonstrate that within the CuPc layer the molecules arrange in two phases and we identify molecular dimers as basic building blocks of the dominant structural phase.