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Plasmonic nanoantennas have attracted much attention lately, among other reasons because of the directionality of light emitted by fluorophores coupled to their localized surface plasmon resonances. Plasmonic picocavities, i.e., cavities with mode volumes below 1 nm3, could act as enhanced antennas due to their extreme field confinement, but the directionality on their emission is difficult to control. In this work, we show that the plasmonic picocavity formed between the tip of a scanning tunneling microscope and a metal surface with a monoatomic step shows directional emission profiles and, thus, can be considered as a realization of a picoantenna. Electromagnetic calculations demonstrate that the observed directionality arises from the reshaping and tilting of the surface charges induced at the scanning tip due to the atomic step. Our results pave the way to exploiting picoantennas as an efficient way for the far-field probing and control of light-matter interactions below the nanoscale. [ABSTRACT FROM AUTHOR]

Doping of a Mott insulator gives rise to a wide variety of exotic emergent states, from high-temperature superconductivity to charge, spin, and orbital orders. The physics underpinning their evolution is, however, poorly understood. A major challenge is the chemical complexity associated with traditional routes to doping. Here, we study the Mott insulating CrO2 layer of the delafossite PdCrO2, where an intrinsic polar catastrophe provides a clean route to doping of the surface. From scanning tunnelling microscopy and angle-resolved photoemission, we find that the surface stays insulating accompanied by a short-range ordered state. From density functional theory, we demonstrate how the formation of charge disproportionation results in an insulating ground state of the surface that is disparate from the hidden Mott insulator in the bulk. We demonstrate that voltage pulses induce local modifications to this state which relax over tens of minutes, pointing to a glassy nature of the charge order. Metallic surface states on CoO2 and Pd terminated surfaces due to electronic reconstruction have been observed in the CoO2-based delafossites. In contrast, here the authors report an interesting insulating state on the CrO2 terminated surface of PdCrO2 due to charge-disproportionation. [ABSTRACT FROM AUTHOR]

Helicenes represent an important class of chiral organic material with promising optoelectronic properties. Hence, functionalization of surfaces with helicenes is a key step towards new organic material devices. This review presents different aspects of adsorption and modification of metal surfaces with different helicene species. Topics addressed are chiral crystallization, that is, 2D conglomerate versus racemate crystallization, breaking of mirror‐symmetry in racemates, chirality‐induced spin selectivity, and stereoselective on‐surface chemistry. [ABSTRACT FROM AUTHOR]

The bottom-up fabrication of supramolecular and self-assembly on various substrates has become an extremely relevant goal to achieve prospects in the development of nanodevices for electronic circuitry or sensors. One of the branches of this field is the self-assembly of functional molecular components driven through non-covalent interactions on the surfaces, such as van der Waals (vdW) interactions, hydrogen bonding (HB), electrostatic interactions, etc., allowing the controlled design of nanostructures that can satisfy the requirements of nanoengineering concepts. In this context, non-covalent interactions present opportunities that have been previously explored in several molecular systems adsorbed on surfaces, primarily due to their highly directional nature which facilitates the formation of well-ordered structures. Herein, we review a series of research works by combining STM (scanning tunneling microscopy) with theoretical calculations, to reveal the processes used in the area of self-assembly driven by molecule Landers equipped with functional groups on the metallic surfaces. Combining these processes is necessary for researchers to advance the self-assembly of supramolecular architectures driven by multiple non-covalent interactions on solid surfaces. [ABSTRACT FROM AUTHOR]

Rare‐earth complexes are vital for separation chemistry and useful in many advanced applications including emission and energy upconversion. Here, 2D rare‐earth clusters having net charges are formed on a metal surface, enabling investigations of their structural and electronic properties on a one‐cluster‐at‐a‐time basis using scanning tunneling microscopy. While these ionic complexes are highly mobile on the surface at ≈100 K, their mobility is greatly reduced at 5 K and reveals stable and self‐limiting clusters. In each cluster, a pair of charged rare‐earth complexes formed by electrostatic and dispersive interactions act as a basic unit, and the clusters are chiral. Unlike other non‐ionic molecular clusters formed on the surfaces, these rare‐earth clusters show mechanical stability. Moreover, their high mobility on the surface suggests that they are in a 2D liquid‐like state. [ABSTRACT FROM AUTHOR]

The adsorption and self-assembly structures of melamine molecules on an Ag(111) surface are studied by low temperature scanning tunneling microscopy (STM) combined with tip-enhanced Raman spectroscopy (TERS). Two ordered self-assembly phases of melamine molecules on Ag(111) were studied by STM and TERS, combining with first-principles simulations. The α-phase consists of flat-lying melamine molecules, while the β-phase consists of mixed up-standing/tilted melamine molecules. Moreover, dehydrogenation of melamine can be controlled by annealing the sample as well as by a tip-enhanced photo-catalytic effect. Our work demonstrates TERS as a powerful tool not only for investigating the configuration and vibration properties of molecules on a metal surface with high spatial resolution but also for manipulating the chemical reactions with tip and photo-induced effects. [ABSTRACT FROM AUTHOR]

BACKGROUND: As a coating material, chitosan can effectively improve biological properties of medical metal surfaces due to its excellent film-forming and metal binding abilities. However, the biological activity and osteoinductive ability of chitosan are insufficient. Graphene oxide can improve the mechanical properties and biocompatibility of various polymer materials, as well as promote osteogenic differentiation. The combination of chitosan and graphene oxide may have better biological properties and osteogenic activity. OBJECTIVE: To construct the graphene oxide-modified chitosan composite coating material, analyze the surface morphology, chemical composition, and physical properties of the coating material, as well as the effects of the coating materials on proliferation, adhesion, and osteogenic differentiation of osteoblasts. METHODS: The titanium surface was treated with 3-aminopropyltriethoxysilane to form silane groups on the surface, and then glutaraldehyde was used to cross-link chitosan with silane groups to prepare simple chitosan coating and graphene oxide/chitosan composite coating, respectively. The surface morphology, chemical structure and hydrophilic properties of the coatings were characterized by atomic force microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, and contact angle measurement system. Rat osteoblasts were seeded on the surface of the two materials, and the proliferation, spreading, and osteogenic differentiation of rat osteoblasts were analyzed by CCK-8 assay, scanning electron microscopy, and reverse transcription-polymerase chain reaction analysis. RESULTS AND CONCLUSION: (1) The thickness of the graphene oxide sheets was about 2 nm as measured by atomic force microscopy; the scanning electron microscopy showed that the surfaces of both coatings were smooth and dense, in which the chitosan molecules were closely arranged and the graphene oxide was uniformly distributed in the chitosan, while wrinkles appeared on the surface of chitosan due to the addition of grapheme. The contact angle of the graphene oxide-chitosan composite coating was significantly smaller than the chitosan coating alone (P < 0.05). (2) CCK-8 assay showed that the graphene oxide-chitosan composite coating better promoted the proliferation of osteoblasts compared with the chitosan coating alone. (3) The scanning electron microscopy showed that better spreading was found in osteoblasts on the surface of the graphene oxide-chitosan composite coating compared with the chitosan coating alone. (4) Reverse transcription-polymerase chain reaction analysis showed that the mRNA expression of alkaline phosphatase and Runx2 was significantly increased in the graphene oxide/chitosan composite coating group compared with in the chitosan coating alone group (P < 0.05). (5) These findings suggest that graphene oxide/chitosan composite coating had good biocompatibility, physicochemical, and osteoinductive properties. [ABSTRACT FROM AUTHOR]

Light emission from the gap of a scanning tunneling microscope can be used to investigate many optoelectronic processes at the single-molecule level and to gain insight into the fundamental photophysical mechanisms involved. One important issue is how to improve the quantum efficiency of quantum emitters in the nanometer-sized metallic gap so that molecule-specific emission can be clearly observed. Here, using electromagnetic simulations, we systematically investigate the influence of an atomic-scale protrusion at the tip apex on the emission properties of a point dipole in the plasmonic nanocavity. We found that such an atomistic protrusion can induce strong and spatially highly confined electric fields, thus increasing the quantum efficiency of molecular fluorescence over two orders of magnitude even when its dipole is oriented parallel to the metal surface, a situation occurring in most realistic single-molecule electroluminescence experiments. In addition, our theoretical simulations indicate that due to the lightning rod effect induced by the protrusion in a plasmonic nanocavity, the quantum efficiency increases monotonically as the tip approaches the dipole to the point of contact, instead of being quenched, thus explaining previous experimental observations with ever-enhancing fluorescence. Furthermore, we also examine in detail how the protrusion radius, height, and material affect the protrusion-induced emission enhancement. These results are believed to be instructive for further studies on the optoelectronic properties of single molecules in tip-based plasmonic nanocavities. [ABSTRACT FROM AUTHOR]

The electrical and mechanical properties of graphene‐based materials can be tuned by the introduction of nanopores, which are sensitively related to the size, morphology, density, and location of nanopores. The synthesis of low‐dimensional graphene nanostructures containing well‐defined nonplanar nanopores has been challenging due to the intrinsic steric hindrance. Herein, we report the selective synthesis of one‐dimensional (1D) graphene nanoribbons (GNRs) containing periodic nonplanar [14]annulene pores on Ag(111) and two‐dimensional (2D) porous graphene nanosheet containing periodic nonplanar [30]annulene pores on Au(111), starting from a same precursor. The formation of distinct products on the two substrates originates from the different thermodynamics and kinetics of coupling reactions. The reaction mechanisms were confirmed by a series of control experiments, and the appropriate thermodynamic and kinetic parameters for optimizing the reaction pathways were proposed. In addition, the combined scanning tunneling spectroscopy (STS) and density functional theory (DFT) calculations revealed the electronic structures of porous graphene structures, demonstrating the impact of nonplanar pores on the π‐conjugation of molecules. [ABSTRACT FROM AUTHOR]

Establishing a general model of heterogeneous ice nucleation has long been challenging because of the surface water structures found on different substrates. Identifying common water clusters, regardless of the underlying substrate, is one of the key steps toward solving this problem. Here, we demonstrate the presence of a common water cluster found on both hydrophilic Pt(111) and hydrophobic Cu(111) surfaces using scanning tunneling microscopy and non-contact atomic force microscopy. Water molecules self-assemble into a structure with a central flat-lying hexagon and three fused pentagonal rings, forming a cluster consisting of 15 individual water molecules. This cluster serves as a critical nucleus during ice nucleation on both surfaces: ice growth beyond this cluster bifurcates to form two-dimensional (three-dimensional) layers on hydrophilic (hydrophobic) surfaces. Our results reveal the inherent similarity and distinction at the initial stage of ice growth on hydrophilic and hydrophobic close-packed metal surfaces; thus, these observations provide initial evidence toward a general model for water-substrate interaction. One key challenge in water science is to create a universal model that can predict the arrangement of water/solid interfaces. Here, the authors use STM and noncontact-AFM to discover common water clusters during the initial growth on hydrophilic and hydrophobic close-packed metal surfaces. [ABSTRACT FROM AUTHOR]

Non‐benzenoid non‐alternant nanographenes (NGs) have attracted increasing attention on account of their distinct electronic and structural features in comparison to their isomeric benzenoid counterparts. In this work, we present a series of unprecedented azulene‐embedded NGs on Au(111) during the attempted synthesis of cyclohepta[def]fluorene‐based high‐spin non‐Kekulé structure. Comprehensive scanning tunneling microscopy (STM) and non‐contact atomic force microscopy (nc‐AFM) evidence the structures and conformations of these unexpected products. The dynamics of the precursor bearing 9‐(2,6‐dimethylphenyl)anthracene and dihydro‐dibenzo‐cyclohepta[def]fluorene units and its reaction products on the surface are analyzed by density functional theory (DFT) and molecular dynamics (MD) simulations. Our study sheds light on the fundamental understanding of precursor design for the fabrication of π‐extended non‐benzenoid NGs on a metal surface. [ABSTRACT FROM AUTHOR]

Superconducting niobium nitride films are ideal candidates for electronics applications among low-Tc materials due to comparatively high critical temperature, large critical magnetic fields and relative ease of fabrication. The superconducting properties of NbN are known to be strongly dependent on the formation of a correct crystallographic phase. The tunneling spectroscopy data for NbN films are in good agreement with existing theoretical concepts, while contact methods provide significantly lower values of the superconducting order parameter. In this paper, we present corresponding results for a representative NbN film with Tc about 14 K, obtained using a point contact made by bringing a sharp metallic tip of silver in touch with the sample surface. We have observed fundamental difference between the gap values extracted from the differential conductance measurements and those following from the standard BCS theory. Despite the almost perfect contact of the normal tip with the film surface, the energy gap was nearly two times smaller than theoretically expected. At the same time, the gap values did not vanish at appreciably lower temperatures compared to the bulk of the NbN film, but rather continued to decrease slowly up to the bulk critical temperature. This finding is explained by significant deformation of the near-surface layer leading to the local suppression of superconducting parameters. Such behavior is a typical example of the superconducting proximity effect when the temperature dependence of the smaller gap strongly deviates from the BCS prediction but remains however finite up to the critical temperature of the larger gap, which is the same for two contacting spaces with superconducting parameters that differ significantly from each other. This conclusion is important for practical applications, in particular, for creating integration circuits based on superconducting NbN thin layers. [ABSTRACT FROM AUTHOR]

Organic semiconductors are prone to strong disorder effects that often exhibit significant dynamic characteristics. In this study, static disorder and dynamic disorder of fullerene molecules at the interface of Au(111) are directly distinguished using Scanning Tunneling Microscopy (STM) and Scanning Tunneling Spectroscopy. We consider an STM image consisting of hundreds of different molecules, as an ensemble which exhibits conductance fluctuations due to both dynamic disorder and static disorder. On the other hand, local conductance measurement of single molecules over time reflects only dynamic disorder. We demonstrate that dynamic disorder is always smaller than static disorder at the C60/Au(111) interface due to structural constraints of molecules at the interface. Dynamic disorder in our experiment is due to small librations of individual molecules that are restricted by the metal surface, while static disorder is related to different bonding orientations of the C60 cage that are frozen-in at room temperature. Our experimental results can be modeled with direct simulations of differential tunneling conductance. [ABSTRACT FROM AUTHOR]

Submolecular resolution scanning tunnelling microscopy and qPlus atomic force microscopy reveal that, close to thermal equilibrium, bi-isonicotinic acid (4,4'-COOH-2,2'-bpy) assembles into extended molecular rows on both Au(111) and Ag(100) surfaces, driven primarily by the formation of OH··· N hydrogen bonds. Both the intermolecular separation and inter-row spacing for Au(111) and Ag(100) are identical within experimental uncertainty, highlighting that the assembly of bi-isonicotinic acid networks on both metal surfaces is predominantly driven by intermolecular hydrogen-bonding and that the potential energy variation due to the substrate has relatively little influence. Nonetheless, the surface plays a key role in molecular organisation: symmetry-breaking induces prochiral behaviour, which drives the molecular enantiomers to form a racemic mixture of rows of different handedness. We adapt a tiling model previously introduced to model the formation of 2D networks of tetracarboxylic derivatives [Blunt et al. Science322, 1077 (2008)] to the bi-isonicotinic acid system, providing key insights into the growth kinetics and attaining good agreement with the molecular morphologies observed in experiment. [ABSTRACT FROM AUTHOR]

The effect of metallic surface contamination on the field electron emission is investigated for the first time using a three dimensional quantum mechanical model. The plane wave periodic version of the density functional theory is used to obtain wavefunctions and potentials. Local and averaged emitted current densities are obtained from them using the time dependent perturbation theory. This method is used to study the effect of the presence of carbon adsorbates on emission from tungsten surfaces. Fowler-Nordheim plots, which provide the dependence of the emitted current with the external electric field, show that carbon contamination inhibits emission. Significant differences with the results of the analytical Fowler-Nordheim model are observed. Emission images (i.e., the spatial dependence of the emitted current density) are presented to identify the important emission spots. These images are significantly different from the electronic density plots usually presented to model constant height scanning tunneling microscope images. Analysis of the emitted current density energy distributions in the light of the projected local density of states provides a deeper understanding of the emission process. [ABSTRACT FROM AUTHOR]

The explorations to extend present chemical synthetic methods are of great importance to simplify synthetic routes of chemical species. Additionally, understanding the chemical reaction mechanisms is critical to achieve controllable synthesis for applications. Here, we report the on-surface visualization and identification of a phenyl group migration reaction of 1,4-dimethyl-2,3,5,6-tetraphenyl benzene (DMTPB) precursor on Au(111), Cu(111) and Ag(110) substrates. With the combination of bond-resolved scanning tunneling microscopy (BR-STM), noncontact atomic force microscopy (nc-AFM) and density functional theory (DFT) calculations, the phenyl group migration reaction of DMTPB precursor is observed, forming various polycyclic aromatic hydrocarbons on the substrates. DFT calculations reveal that the multiple-step migrations are facilitated by the hydrogen radical attack, inducing cleavage of phenyl groups and subsequent rearomatization of the intermediates. This study provides insights into complex surface reaction mechanisms at the single molecule level, which may guide the design of chemical species. On-surface synthesis allows fabrication of nanostructures with atomic precision and may follow different routes compared to in-solution chemistry. Here the authors, using scanning probe microscopy techniques, observe a phenyl group migration reaction on three different metal surfaces forming polycyclic aromatic hydrocarbons, which cannot be accessed by in-solution chemistry. [ABSTRACT FROM AUTHOR]

Largish molecules on metal surfaces may act as not only the building blocks of 2D self-assemblies, but also as the template to reshape the metal surfaces. Here, we report the molecular adsorption-induced formation of the periodic nanostripe arrays of substrate atoms through long-range mass transport. When adsorbed on the close-packed Cd(0001) surface, the triphenyl bismuth (TPB) molecules form a 2D self-assembly with 4 × √13 reconstruction. Simultaneously, periodic nanostripe arrays of Cd atoms appear on the substrate terraces. High-resolution scanning tunneling microscopy (STM) images indicate that the Cd nanostrips are built from the parallel segments of Cd atomic chains with 2 × 2 reconstruction. In the mixed phase, the Cd atomic chains exhibit only high-order commensuration when situated between two molecular domains. The massive structural rearrangement of the Cd(0001) surface can be attributed to a strong molecule–substrate interaction. [ABSTRACT FROM AUTHOR]

The delicate balance between hydrogen bonding and van der Waals interactions determines the stability, structure, and chirality of many molecular and supramolecular aggregates weakly adsorbed on solid surfaces. Yet the inherent complexity of these systems makes their experimental study at the molecular level very challenging. In this quest, small alcohols adsorbed on metal surfaces have become a useful model system to gain fundamental insight into the interplay of such molecule-surface and molecule-molecule interactions. Here, through a combination of scanning tunneling microscopy and density functional theory, we compare and contrast the adsorption and self-assembly of a range of small alcohols from methanol to butanol on Au(111). We find that longer chained alcohols prefer to form zigzag chains held together by extended hydrogen bonded networks between adjacent molecules. When alcohols bind to a metal surface datively via one of the two lone electron pairs of the oxygen atom, they become chiral. Therefore, the chain structures are formed by a hydrogen-bonded network between adjacent molecules with alternating adsorbed chirality. These chain structures accommodate longer alkyl tails through larger unit cells, while the position of the hydroxyl group within the alcohol molecule can produce denser unit cells that maximize intermolecular interactions. Interestingly, when intrinsic chirality is introduced into the molecule as in the case of 2-butanol, the assembly changes completely and square packing structures with chiral pockets are observed. This is rationalized by the fact that the intrinsic chirality of the molecule directs the chirality of the adsorbed hydroxyl group meaning that heterochiral chain structures cannot form. Overall this study provides a general framework for understanding the effect of simple alcohol molecular adstructures on hydrogen bonded aggregates and paves the way for rationalizing 2D chiral supramolecular assembly. [ABSTRACT FROM AUTHOR]

Complexes containing rare-earth ions attract great attention for their technological applications ranging from spintronic devices to quantum information science. While charged rare-earth coordination complexes are ubiquitous in solution, they are challenging to form on materials surfaces that would allow investigations for potential solid-state applications. Here we report formation and atomically precise manipulation of rare-earth complexes on a gold surface. Although they are composed of multiple units held together by electrostatic interactions, the entire complex rotates as a single unit when electrical energy is supplied from a scanning tunneling microscope tip. Despite the hexagonal symmetry of the gold surface, a counterion at the side of the complex guides precise three-fold rotations and 100% control of their rotational directions is achieved using a negative electric field from the scanning probe tip. This work demonstrates that counterions can be used to control dynamics of rare-earth complexes on materials surfaces for quantum and nanomechanical applications. Rare-earth elements are vital to advanced technological applications ranging from spintronic devices to quantum information science. Here, the authors formed charged rare-earth complexes on a material surface and demonstrated atomically precise control on their rotational dynamics. [ABSTRACT FROM AUTHOR]

The synthesis of long n‐peri‐acenes (n‐PAs) is challenging as a result of their inherent open‐shell radical character, which arises from the presence of parallel zigzag edges beyond a certain n value. They are considered as π‐electron model systems to study magnetism in graphene nanostructures; being potential candidates in the fabrication of optoelectronic and spintronic devices. Here, we report the on‐surface formation of the largest pristine member of the n‐PA family, i.e. peri‐heptacene (n=7, 7‐PA), obtained on an Au(111) substrate under ultra‐high vacuum conditions. Our high‐resolution scanning tunneling microscopy investigations, complemented by theoretical simulations, provide insight into the chemical structure of this previously elusive compound. In addition, scanning tunneling spectroscopy reveals the antiferromagnetic open‐shell singlet ground state of 7‐PA, exhibiting singlet–triplet spin‐flip inelastic excitations with an effective exchange coupling (Jeff) of 49 meV. [ABSTRACT FROM AUTHOR]

A detailed understanding of the dissociation of O2 molecules on metal surfaces induced by various excitation sources, electrons/holes, light, and localized surface plasmons, is crucial not only for controlling the reactivity of oxidation reactions but also for developing various oxidation catalysts. The necessity of mechanistic studies at the single‐molecule level is increasingly important for understanding interfacial interactions between O2 molecules and metal surfaces and to improve the reaction efficiency. We review single‐molecule studies of O2 dissociation on Ag(110) induced by various excitation sources using a scanning tunneling microscope (STM). The comprehensive studies based on the STM and density functional theory calculations provide fundamental insights into the excitation pathway for the dissociation reaction. [ABSTRACT FROM AUTHOR]

The development of widely applicable methods for the synthesis of C-C-bonded nanostructures on inert and insulating surfaces is a challenging yet rewarding milestone in the field of on-surface synthesis. This would enable studies of nearly unperturbed covalent nanostructures with unique electronic properties as graphene nanoribbons (GNR) and π-conjugated 2D polymers. The prevalent Ullmann-type couplings are almost exclusively carried out on metal surfaces to lower the temperature required for initial dehalogenation well below the desorption threshold. To overcome the necessity for the activation of monomers on the target surface, we employ a recently developed Radical Deposition Source (RaDeS) for the direct deposition of radicals onto inert surfaces for subsequent coupling by addition reactions. The radicals are generated en route by indirect deposition of halogenated precursors through a heated reactive tube, where the dehalogenation reaction proceeds. Here, we use the ditopic 6,11-diiodo-1,2,3,4-tetraphenyltriphenylene (DITTP) precursor that afforded chevron-like GNR on Au(111) via the usual two-staged reaction comprised of monomer-coupling into covalent polymers and subsequent formation of an extended GNR by intramolecular cyclodehydrogenation (CDH). As a model system for inert surfaces, we use Ag(111) passivated with a closed monolayer of chemisorbed iodine that behaves in an inert manner with respect to dehalogenation reactions and facilitates the progressive coupling of radicals into extended covalent structures. We deposit the DITTP-derived biradicals onto both iodine-passivated and pristine Ag(111) surfaces. While on the passivated surface, we directly observe the formation of covalent polymers, on pristine Ag(111) organometallic intermediates emerge instead. This has decisive consequences for the further progression of the reaction: heating the organometallic chain directly on Ag(111) results in complete desorption, whereas the covalent polymer on iodine-passivated Ag(111) can be transformed into the GNR. Yet, the respective CDH proceeds directly on Ag(111) after thermal desorption of the iodine passivation. Accordingly, future work is aimed at the further development of approaches for the complete synthesis of GNR on inert surfaces. [ABSTRACT FROM AUTHOR]

The determination of the configuration of atomic adsorbates on clean metal surfaces has been a key issue in surface science 60 years ago and still is today. We demonstrate that despite the prevalence of combined scanning tunneling microscopy and density functional theory studies of adsorbate systems the pitfalls are plentiful calling for accurate, reliable structure analyses that can be delivered by diffraction methods. We analyze and compare the ordered phases of Te on Ir(111), Ir(100), and Au(100) demonstrating the accuracy, the in-depth information and physical insight that can nowadays be obtained by quantitative low-energy electron diffraction structural analyses. • The atomic structures of six ordered tellurium adsorbate phases are determined. • Analysis shows adatom repulsion, significantly mediated by the substrate. • The degree of order of the phases depends on elastic properties of the substrates. [Display omitted] [ABSTRACT FROM AUTHOR]

In this review, we give an overview on the spin crossover of Fe(phen)2(NCS)2 complexes adsorbed on Cu(100), Cu2N/Cu(100), Cu(111), Co/Cu(111), Co(100), Au(100), and Au(111) surfaces. Depending on the strength of the interaction of the molecules with the substrates, the spin crossover behavior can be drastically changed. Molecules in direct contact with non-magnetic metallic surfaces coexist in both the high- and low-spin states but cannot be switched between the two. Our analysis shows that this is due to a strong interaction with the substrate in the form of a chemisorption that dictates the spin state of the molecules through its adsorption geometry. Upon reducing the interaction to the surface either by adding a second molecular layer or inserting an insulating thin film of Cu2N, the spin crossover behavior is restored and molecules can be switched between the two states with the help of scanning tunneling microscopy. Especially on Cu2N, the two states of single molecules are stable at low temperature and thus allow the realization of a molecular memory. Similarly, the molecules decoupled from metallic substrates in the second or higher layers display thermally driven spin crossover as has been revealed by X-ray absorption spectroscopy. Finally, we discuss the situation when the complex is brought into contact with a ferromagnetic substrate. This leads to a strong exchange coupling between the Fe spin in the high-spin state and the magnetization of the substrate as deduced from spin-polarized scanning tunneling spectroscopy and ab initio calculation. [ABSTRACT FROM AUTHOR]

We present the design, implementation, and illustrative results of a light collection/injection strategy based on an off-axis parabolic mirror collector for a low-temperature Scanning Tunneling Microscope (STM). This device allows us to perform STM induced Light Emission (STM-LE) and Cathodoluminescence (STM-CL) experiments and in situ Photoluminescence (PL) and Raman spectroscopy as complementary techniques. Considering the Étendue conservation and using an off-axis parabolic mirror, it is possible to design a light collection and injection system that displays 72% of collection efficiency (considering the hemisphere above the sample surface) while maintaining high spectral resolution and minimizing signal loss. The performance of the STM is tested by atomically resolved images and scanning tunneling spectroscopy results on standard sample surfaces. The capabilities of our system are demonstrated by performing STM-LE on metallic surfaces and two-dimensional semiconducting samples, observing both plasmonic and excitonic emissions. In addition, we carried out in situ PL measurements on semiconducting monolayers and quantum dots and in situ Raman on graphite and hexagonal boron nitride (h-BN) samples. Additionally, STM-CL and PL were obtained on monolayer h-BN gathering luminescence spectra that are typically associated with intragap states related to carbon defects. The results show that the flexible and efficient light injection and collection device based on an off-axis parabolic mirror is a powerful tool to study several types of nanostructures with multiple spectroscopic techniques in correlation with their morphology at the atomic scale and electronic structure. [ABSTRACT FROM AUTHOR]

The rational fabrication of low-dimensional materials with a well-defined topology and functions is an incredibly important aspect of nanotechnology. In particular, the on-surface synthesis (OSS) methods based on the bottom-up approach enable a facile construction of sophisticated molecular architectures unattainable by traditional methods of wet chemistry. Among such supramolecular constructs, especially interesting are the surface-supported metal–organic networks (SMONs), composed of low-coordinated metal atoms and π -aromatic bridging linkers. In this work, the lattice Monte Carlo (MC) simulation technique was used to extract the chemical information encoded in a family of Y-shaped positional isomers co-adsorbed with trivalent metal atoms on a flat metallic surface with (111) geometry. Depending on the intramolecular distribution of active centers (within the simulated molecular bricks, we observed a metal-directed self-assembly of two-dimensional (2D) openwork patterns, aperiodic mosaics, and metal–organic ladders. The obtained theoretical findings could be especially relevant for the scanning tunneling microscopy (STM) experimentalists interested in a surface-assisted construction of complex nanomaterials stabilized by directional coordination bonds. [ABSTRACT FROM AUTHOR]

Self‐assembly of cyclohexyl cyclic (alkyl)(amino)carbenes (cyCAAC) can be realized and reversibly switched from a close‐packed trimer phase to a chainlike dimer phase, enabled by the ring‐flip of the cyclohexyl wingtip. Multiple methods including scanning tunneling microscopy (STM), X‐ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations identified a distinct isomer (axial or equatorial chair conformer) in each phase, and consequently support the conclusion regarding the determination of molecular surface geometry on the self‐assembly of cyCAAC. Moreover, various substrates such as Ag (111) and Cu (111) are tested to elucidate the importance of cyCAAC‐surface interactions on cyCAAC based nanopatterns. These investigations of patterned surfaces prompted a deep understanding of cyCAAC binding mode, surface geometry and reversible self‐assembly, which are of paramount significance in the areas of catalysis, biosensor design and surface functionalization. [ABSTRACT FROM AUTHOR]

Understanding the growth behavior of group‐V elements on metal surfaces provides valuable information that can shed light on the feasibility of tailoring atomically thin monoelemental 2D polymorphs composed of pnictogens on these metallic substrates. Here, by combining scanning tunneling microscopy (STM), low energy electron diffraction and Auger electron spectroscopy measurements under ultra‐high vacuum conditions, a wide variety of Sb reconstructions on single‐crystal Pt(111) are identified and characterized. At Sb coverage of ≈0.2 ML, STM data are compatible with a scenario in which Sb atoms are randomly embedded into the topmost layer of Pt, in a substitutional configuration and without establishing a periodic structure. This disorder is robust against thermal annealing and quenching. Increasing the surface coverage and whether or not the sample is annealed, different well‐ordered Sb phases are formed. The Sb structures synthesized at room temperature without any heating process are best interpreted as surface alloys that involve only the first atomic layer. In contrast, experimental evidence points towards the development of multilayer alloy phases for the annealed samples. [ABSTRACT FROM AUTHOR]

A set of dipolar molecular rotor compounds was designed, synthesized and adsorbed as self‐assembled 2D arrays on Ag(111) surfaces. The title molecules are constructed from three building blocks: (a) 4,8,12‐trioxatriangulene (TOTA) platforms that are known to physisorb on metal surfaces such as Au(111) and Ag(111), (b) phenyl groups attached to the central carbon atom that function as pivot joints to reduce the barrier to rotation, (c) pyridine and pyridazine units as small dipolar units on top. Theoretical calculations and scanning tunneling microscopy (STM) investigations hint at the fact that the dipoles of neighboring rotors interact through space through pairs of energetically favorable head‐to‐tail arrangements. [ABSTRACT FROM AUTHOR]

We present scanning tunneling microscopy and spectroscopy (STM/STS) investigations of the electronic structures of different alkyl-substituted oligothiophenes on the Au(111) surface. STM imaging showed that on Au(111), oligothiophenes adopted distinct straight and bent conformations. By combining STS maps with STM images, we visualize, in real space, particle-in-a-box-like oligothiophene molecular orbitals. We demonstrate that different planar conformers with significant geometrical distortions of oligothiophene backbones surprisingly exhibit very similar electronic structures, indicating a low degree of conformation-induced electronic disorder. The agreement of these results with gas-phase density functional theory calculations implies that the oligothiophene interaction with the Au(111) surface is generally insensitive to molecular conformation. [ABSTRACT FROM AUTHOR]

The adsorption of oxygen and the resultant O-induced surface reconstructions are key components in heterogeneously catalyzed reactions on silver metal surfaces. O uptake and reconstructions on planar Ag(111) are well-characterized, and in this paper, we show that curved Ag(111) features similar O adsorption and reconstructions. Through a systematic scanning tunneling microscope study of a curved Ag(111) single crystal exposed to gas-phase atomic oxygen at a temperature of 525 K, we observed O a d and, upon higher coverages, saw p(4 × 4) and p(4 × 5 √ 3) reconstructions form on both the A-type and B-type steps. Exposures at low temperatures (< 500 K) resulted in the formation of subsurface oxygen and the appearance of a stripe pattern and amorphous phase on the surface. Upon heating, stable surface reconstructions were formed. Although the geometric arrangement of atoms along the steps were different, A-type and B-type steps formed the same reconstructions. In addition, the B-type steps also saw the formation of several different features atop the oxygen reconstructions. [ABSTRACT FROM AUTHOR]

The adsorption and self-assembled structures of a-sexithiophene (α-6T) have been investigated on a Si(111)-Ag surface using scanning tunneling microscopy (STM), low-energy electron diffraction, and density functional theory calculations. The adsorbed α-6T molecules are arranged into unidirectional molecular rows with a side-by-side orientation. The molecular rows reveal three kinds of appearances in the filled-state STM images, which reflect the distinct adsorption sites. From tunneling spectroscopy, we find that the filled-state STM images of &3945;-6T should be influenced by the surface states of Si(111)-Ag. At one monolayer coverage, sequentially ordering of the triple molecular rows results in the close-packed arrangement of the α-6T overlayer. [ABSTRACT FROM AUTHOR]

The role of dipole-dipole interactions in the self-assembly of dipolar organic molecules on surfaces is investigated. As a model system, strongly dipolar model molecules, p-benzoquinonemonoimine zwitterions (ZI) of type C6H2(...NHR)2(...O)2 on crystalline coinage metal surfaces were investigated with scanning tunneling microscopy and first principles calculations. Depending on the substrate, the molecules assemble into small clusters, nano gratings, and stripes, as well as in two-dimensional islands. The alignment of the molecular dipoles in those assemblies only rarely assumes the lowest electrostatic energy configuration. Based on calculations of the electrostatic energy for various experimentally observed molecular arrangements and under consideration of computed dipole moments of adsorbed molecules, the electrostatic energy minimization is ruled out as the driving force in the self-assembly. The structures observed are mainly the result of a competition between chemical interactions and substrate effects. The substrate's role in the self-assembly is to (i) reduce and realign the molecular dipole through charge donation and back donation involving both the molecular HOMO and LUMO, (ii) dictate the epitaxial orientation of the adsorbates, specifically so on Cu(111), and (iii) inhibit attractive forces between neighboring chains in the system ZI/Cu(111), which results in regularly spaced molecular gratings. [ABSTRACT FROM AUTHOR]

Serpentine chain C60 phases were observed in scanning tunneling microscopy (STM) images of C60 layers on zinc phthalocyanine (ZnPc) or pentacene covered Ag(111) and Au(111) surfaces. This low-density, quasi-one-dimensional organization contrasts starkly with the close-packed hexagonal phases observed for C60 layers on bare metal substrates. STM was employed to perform a detailed investigation of these chain structures for C60/ZnPc/Ag(111) heterolayers. Motivated by the similarity of these chain phases, and the chain and stripe organization occurring in dipole-fluid systems, we investigated a model based on competing van der Waals attractions and electrostatic repulsions between C60 molecules as an explanation for the driving force behind these monolayer phases. Density functional theory (DFT) calculations revealed significant charge transfer to C60 from the Ag(111) substrate, through the intervening ZnPc layer, inducing electrostatic interactions between C60 molecules. Molecular dynamics simulations performed with attractive van derWaals interactions plus repulsive dipole-dipole interactions reproduced the C60 chain phases with dipole magnitudes consistent with DFT calculations. [ABSTRACT FROM AUTHOR]

Among the plethora of polycyclic structures that have emerged in recent years, indenofluorenes comprise a unique class of compounds due to their potential in organic electronic systems such as OLEDs, OFETs, and OPVCs. However, the synthesis of fully conjugated indenofluorenes without bulky groups on the apical carbons under standard chemistry conditions is not easily accessible. In this regard, on-surface synthesis has appeared as a newly developing field of research, which exploits the use of well-defined solid surfaces as confinement templates to initiate and develop chemical reactions. Here, we demonstrate the successful fabrication of indeno[1,2-b]fluorene π-conjugated polymers linked via cumulene-like connections on well-defined metallic surfaces under ultra-high vacuum conditions. The structure and electronic properties of the formed polymers have been precisely characterized by scanning tunneling microscopy, noncontact atomic force microscopy and scanning tunneling spectroscopy, complemented by computational investigations. [ABSTRACT FROM AUTHOR]

Experimental scanning tunneling microscopy (STM) studies have shown for more than two decades rectangular formations when sulfur atoms are deposited on Au(111) surfaces. The precursors have ranged from simple molecules or ions, such as SO2 gas or sulfide anions, to more complex organosulfur compounds. We investigated, within the framework of the Density Functional Theory, the structure of these rectangular patterns assuming them entirely composed of sulfur atoms as the experimental evidence suggests. The sulfur coverage at which the simulations were carried out (0.67 ML or higher) provoked that the sulfur-sulfur association had to be taken into account for achieving a good agreement between the sets of simulated and experimental STM images. A combination of four sulfur dimers per rectangular formation properly explained the trends obtained by the experimental STM analysis which were related with the rectangles' size and shape fluctuations together with sulfur-sulfur distances within these rectangles. Finally, a projected density of states analysis showed that the dimers were capable of altering the Au(5d) electronic states at the same level as atomic sulfur adsorbed at low coverage. Besides, sulfur dimers states were perfectly distinguished, whose presence near and above the Fermi level can explain both: sulfur-sulfur bond elongation and dimers stability when they stayed adsorbed on the surface at high coverage. [ABSTRACT FROM AUTHOR]

Silicene, a new 2D material has attracted intense research because of the ubiquitous use of silicon in modern technology. However, producing free‐standing silicene has proved to be a huge challenge. Until now, silicene could be synthesized only on metal surfaces where it naturally forms strong interactions with the metal substrate that modify its electronic properties. Here, the authors report the first experimental evidence of silicene nanoribbons on an insulating NaCl thin film. This work represents a major breakthrough, for the study of the intrinsic properties of silicene, and by extension to other 2D materials that have so far only been grown on metal surfaces. [ABSTRACT FROM AUTHOR]

The formation of azo compounds via redox cross‐coupling of nitroarenes and arylamines, challenging in solution phase chemistry, is achieved by on‐surface chemistry. Reaction products are analyzed with a cryogenic scanning tunneling microscope (STM) and X‐ray photoelectron spectroscopy (XPS). By using well‐designed precursors containing both an amino and a nitro functionality, azo polymers are prepared on surface via highly efficient nitro‐amino cross‐coupling. Experiments conducted on other substrates and surface orientations reveal that the metal surface has a significant effect on the reaction efficiency. The reaction was further found to proceed from partially oxidized/reduced precursors in dimerization reactions, shedding light on the mechanism that was studied by DFT calculations. [ABSTRACT FROM AUTHOR]

The interaction at the molecular level of the spin‐crossover (SCO) FeII((3,5‐(CH3)2Pz)3BH)2 complex with the Au(111) surface is analyzed by means of rPBE periodic calculations. Our results show that the adsorption on the metallic surface enhances the transition energy, increasing the relative stability of the low spin (LS) state. The interaction indeed is spin‐dependent, stronger for the low spin than the high spin (HS) state. The different strength of the Fe ligand field at low and high temperature manifests on the nature, spatial extension and relative energy of the states close to the Fermi level, with a larger metal–ligand hybridization in the LS state. This feature is of relevance for the differential adsorption of the LS and HS molecules, the spin‐dependent conductance, and for the differences found in the corresponding STM images, correctly reproduced from the density of states provided by the rPBE calculations. It is expected that this spin dependence will be a general feature of the SCO molecule–substrate interaction, since it is rooted in the different ligand field of Fe site at low and high temperatures, a common hallmark of the FeII SCO complexes. Finally, the states involved in the LIESST phenomenon has been identified through NEVPT2 calculations on a model reaction path. A tentative pathway for the photoinduced LS→HS transition is proposed, that does not involve the intermediate triplet states, and nicely reproduces both the blue laser wavelength required for the activation, and the wavelength of the reverse HS → LS transition. [ABSTRACT FROM AUTHOR]

A model for treating excitation and relaxation of adsorbates at metallic surfaces induced by non-adiabatic coupling is developed. The derivation is based on the concept of resonant electron transfer, where the adsorbate serves as a molecular bridge for the inelastic transition between an electron source and a sink. In this picture, energy relaxation and scanning tunneling microscopy (STM) at metallic surfaces are treated on an equal footing as a quasi-thermal process. The model goes beyond the local harmonic approximation and allows for an unbiased description of floppy systems with multiple potential wells. Further, the limitation of the product ansatz for the vibronic wave function to include the position-dependence of the non-adiabatic couplings is avoided by explicitly enforcing detailed balance. The theory is applied to the excitation of hydrogen on palladium, which has multiple local potential minima connected by low energy barriers. The main aspects investigated are the lifetimes of adsorbate vibrations in different adsorption sites, as well as the dependence of the excitation, response, and transfer rates on an applied potential bias. The excitation and relaxation simulations reveal intricate population dynamics that depart significantly from the simplistic tunneling model in a truncated harmonic potential. In particular, the population decay from an initially occupied local minimum induced by the contact with an STM tip is found to be better described by a double exponential. The two rates are interpreted as a response to the system perturbation and a transfer rate following the perturbation. The transfer rate is found to obey a power law, as was the case in previous experimental and theoretical work. [ABSTRACT FROM AUTHOR]

At low coverage of water on Cu(110), substrate-mediated electrostatics lead to zigzagging chains along [001] as observed with STM [T. Yamada, S. Tamamori, H. Okuyama, and T. Aruga, 'Anisotropic water chain growth on Cu(110) observed with scanning tunneling microscopy' Phys. Rev. Lett. 96, 036105 (2006)]. Using x-ray absorption spectroscopy we find an anomalous low-energy resonance at ∼533.1 eV which, based on density functional theory spectrum simulations, we assign to an unexpected configuration of water units whose uncoordinated O-H bonds directly face those of their neighbors; this interaction repeats over trough sites with enhanced electron density and is analogous to the case of a hydrated electron. [ABSTRACT FROM AUTHOR]

Thiolate coordination networks (TCNs) were synthesized on metal surfaces using benzenehexathiol (BHT) and analyzed by cryogenic scanning tunneling microscopy (STM), X‐ray photoelectron spectroscopy (XPS) as well as density functional theory. Upon adsorption, the deprotonation of the thiol groups occurred on the metal surface with the formation of metal‐sulfur coordination bonds. Increasing the surface temperature triggered the complete dehydrogenation of BHT and promoted the formation of TCNs. On Ag(111), the TCN of [Ag3(C6S6)]n was achieved and showed good thermal stability. On Cu(111), two TCNs ([Cu6(C6S6)]n and [Cu8(C6S6)]n,) were identified. Interestingly, the construction of the two TCNs on Cu(111) can be precisely controlled by adjusting the temperature of the surface during deposition and thermal annealing. Our results reveal the significant influence of the metal surface on the formation of coordination networks. [ABSTRACT FROM AUTHOR]

We report on the synthesis and characterization of atomically precise one‐dimensional diradical peripentacene polymers on a Au(111) surface. By means of high‐resolution scanning probe microscopy complemented by theoretical simulations, we provide evidence of their magnetic properties, which arise from the presence of two unpaired spins at their termini. Additionally, we probe a transition of their magnetic properties related to the length of the polymer. Peripentacene dimers exhibit an antiferromagnetic (S=0) singlet ground state. They are characterized by singlet–triplet spin‐flip inelastic excitations with an effective exchange coupling (Jeff) of 2.5 meV, whereas trimers and longer peripentacene polymers reveal a paramagnetic nature and feature Kondo fingerprints at each terminus due to the unpaired spin. Our work provides access to the precise fabrication of polymers featuring diradical character which are potentially useful in carbon‐based optoelectronics and spintronics. [ABSTRACT FROM AUTHOR]

Porphyrins are a versatile class of molecules, which have attracted attention over the years due to their electronic, optical and biological properties. Self-assembled monolayers of porphyrins were widely studied on metal surfaces in order to understand the supramolecular organization of these molecules, which is a crucial step towards the development of devices starting from the bottom-up approach. This perspective could lead to tailor the interfacial properties of the surface, depending on the specific interaction between the molecular assembly and the metal surface. In this study, we revisit the investigation of the assembly of zinc-tetraphenylporphyrins on Au(111) in order to explore the adsorption of the molecular network on the noble metal substrate. The combined analysis of scanning tunneling microscopy (STM) imaging and core levels photoemission spectroscopy measurements support a peculiar arrangement of the ZnTPP molecular network, with Zn atoms occupying the bridge sites of the Au surface atoms. Furthermore, we prove that, at few-layers coverage, the interaction between the deposited layers allows a relevant molecular mobility of the adlayer, as observed by STM and supported by core levels photoemission analysis. [ABSTRACT FROM AUTHOR]

Resolution of enantiomers of chiral compounds via crystallization is the dominant method in chemical industry, but chiral recognition at the molecular level during this process is still poorly understood. Using single metal surfaces in ultrahigh vacuum as model system, the enantio‐related transition from the monolayer structure into a double layer of the racemic mixture of heptahelicene has been studied with scanning tunneling microscopy. Submolecular resolution reveals enantiopure second layers on Ag(111) and almost enantiopure second layers on Au(111). In analogy to previous results on Cu(111), it is concluded that transition from the 2D first layer racemate into a layered racemate occurs. [ABSTRACT FROM AUTHOR]

Adsorption of chalcogen atoms on metal surfaces has attracted increasing interest for both the fundamental research and industrial applications. Here, we report a systematic study of selenium (Se) adsorption on Au(111) at varies substrate temperatures by scanning tunneling microscopy. At room temperature, small Se clusters are randomly dispersed on the surface. Increasing the temperature up to 200 °C, a well-ordered lattice of Se molecules consisting of 8 Se atoms in ring-like structure is formed. Further increasing the temperature to 250 °C gives rise to the formation of Se monolayer with Au(111)- lattices superimposed with a quasi-hexagonal lattice. Desorption of Se atoms rather than the reaction between the Se atoms and the Au substrate occurs if further increasing the temperature. The ordered structures of selenium monolayers could serve as templates for self-assemblies and our findings in this work might provide insightful guild for the epitaxial growth of the two-dimensional transition metal dichalcogenides. [ABSTRACT FROM AUTHOR]

An operando investigation of graphene growth on (100) grains of polycrystalline nickel (Ni) surfaces was performed by means of variable-temperature scanning tunneling microscopy complemented by density functional theory simulations. A clear description of the atomistic mechanisms ruling the graphene expansion process at the stepped regions of the substrate is provided, showing that different routes can be followed, depending on the height of the steps to be crossed. When a growing graphene flake reaches a monoatomic step, it extends jointly with the underlying Ni layer; for higher Ni edges, a different process, involving step retraction and graphene landing, becomes active. At step bunches, the latter mechanism leads to a peculiar 'staircase formation' behavior, where terraces of equal width form under the overgrowing graphene, driven by a balance in the energy cost between C–Ni bond formation and stress accumulation in the carbon layer. Our results represent a step towards bridging the material gap in searching new strategies and methods for the optimization of chemical vapor deposition graphene production on polycrystalline metal surfaces. Image 1 [ABSTRACT FROM AUTHOR]

Among the prerequisites for the progress of single‐molecule‐based electronic devices are a better understanding of the electronic properties at the individual molecular level and the development of methods to tune the charge transport through molecular junctions. Scanning tunneling microscopy (STM) is an ideal tool not only for the characterization, but also for the manipulation of single atoms and molecules on surfaces. The conductance through a single molecule can be measured by contacting the molecule with atomic precision and forming a molecular bridge between the metallic STM tip electrode and the metallic surface electrode. The parameters affecting the conductance are mainly related to their electronic structure and to the coupling to the metallic electrodes. Here, the experimental and theoretical analyses are focused on single tetracenothiophene molecules and demonstrate that an in situ‐induced direct desulfurization reaction of the thiophene moiety strongly improves the molecular anchoring by forming covalent bonds between molecular carbon and copper surface atoms. This bond formation leads to an increase of the conductance by about 50 % compared to the initial state. [ABSTRACT FROM AUTHOR]

Atomically-sharp tips in close proximity of metal surfaces create plasmonic nanocavities supporting both radiative (bright) and non-radiative (dark) localized surface plasmon modes. Disentangling their respective contributions to the total density of optical states remains a challenge. Electroluminescence due to tunnelling through the tip-substrate gap could allow the identification of the radiative component, but this information is inherently convoluted with that of the electronic structure of the system. In this work, we present a fully experimental procedure to eliminate the electronic-structure factors from the scanning tunnelling microscope luminescence spectra by confronting them with spectroscopic information extracted from elastic current measurements. Comparison against electromagnetic calculations demonstrates that this procedure allows the characterization of the meV shifts experienced by the nanocavity plasmonic modes under atomic-scale gap size changes. Therefore, the method gives access to the frequency-dependent radiative Purcell enhancement that a microscopic light emitter would undergo when placed at such nanocavity. Disentangling the radiative and non-radiative plasmon mode contributions to the total photonic density of states is a challenge. Here, the authors report a procedure to eliminate the electronic-structure factors from scanning tunnelling microscope luminescence spectra to isolate the radiative component. [ABSTRACT FROM AUTHOR]

Density functional theory is used to simulate high-bias, constant-current scanning tunneling micrographs for direct comparison with experimental images. Coupled to previous spectroscopic data, these simulations are used to determine the atomic structure of Ti-rich nanostructures on strontium titanate (001) surfaces. These nanostructures have three consecutive TiOx surface layers and exploit the distinctive structural motif of the c(4 × 2) reconstruction as their main building block. A structural model of a characteristic triline defect is also proposed. [ABSTRACT FROM AUTHOR]