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Interfacial complex supramolecular tessellations were employed to derive novel two-dimensional electronic structures from Shockley surface-state, giving rise to Kagome or Dirac bands as well as hybrid band structures through quantum dots coupling.

One-dimensional (1D) metal–organic (MO) nanowires are captivating from fundamental and technological perspectives due to their distinctive magnetic and electronic properties. The solvent-free synthesis of such nanomaterials on catalytic surfaces provides a unique approach for fabricating low-dimensional single-layer materials with atomic precision and low amount of defects. A detailed understanding of the electronic structure of MO polymers such as band gap and dispersive bands is critical for their prospective implementation into nanodevices such as spin sensors or field-effect transistors. Here, we have performed the on-surface reaction of quinoidal ligands with single cobalt atoms (Co-QDI) on a vicinal Au(788) surface in ultra-high vacuum. This procedure promotes the growth and uniaxial alignment of Co-QDI MO chains along the surface atomic steps, while permitting the mapping of their electronic properties with space-averaging angle-resolved photoemission spectroscopy. In the direction parallel to the principal chain axis, a well-defined 1D band structure with weakly dispersive and dispersive bands is observed, confirming a pronounced electron delocalization. Low-temperature scanning tunneling microscopy/spectroscopy delves into the atomically precise structure of the nanowires and elucidates their narrow bandgap. These findings are supported with GW0 band structure calculations showing that the observed electronic bands emanate from the efficient hybridization of Co(3d) and molecular orbitals. Our work paves the way towards a systematic search of similar 1D π–d hybridized MO chains with tunable electronic and magnetic properties defined by the transition or rare earth metal atom of choice., Financial support was provided from the Spanish Research Council CSIC through I-LINK C20002; grants PID2019-107338RB-C63, PID2019-103910GB-100 and PID2020-116093RB-C44 funded by MCIN/AEI/10.13039/501100011033. We further thank support from the Basque Government, grants IT-1591-22, IT-1527-22, IT-1246-19 and IT-1260-19 as well as Universidad del País Vasco grant GIU18/138.

Surfaces are at the frontier of every known solid. They provide versatile supports for functional nanostructures and mediate essential physicochemical processes. Intimately related to two-dimensional materials, interfaces and atomically thin films often feature distinct electronic states with respect to the bulk, which is key to many relevant properties, such as catalytic activity, interfacial charge-transfer, and crystal growth mechanisms. To induce novel quantum properties via lateral scattering and confinement, reducing the surface electrons’ dimensionality and spread with atomic precision is of particular interest. Both atomic manipulation and supramolecular principles provide access to custom-designed molecular assemblies and superlattices, which tailor the surface electronic landscape and influence fundamental chemical and physical properties at the nanoscale. Here the confinement of surface-state electrons is reviewed, with a focus on their interaction with molecular scaffolds created by molecular manipulation and self-assembly protocols under ultrahigh vacuum conditions. Starting with the quasifree two-dimensional electron gas present at the (111)-oriented surface planes of noble metals, the intriguing molecule-based structural complexity and versatility is illustrated. Surveyed are low-dimensional confining structures in the form of artificial lattices, molecular nanogratings, or quantum dot arrays, which are constructed upon an appropriate choice of their building constituents. Whenever the realized (metal-)organic networks exhibit long-range order, modified surface band structures with characteristic features emerge, inducing noteworthy physical phenomena such as discretization, quantum coupling or energy, and effective mass renormalization. Such collective electronic states can be additionally modified by positioning guest species at the voids of open nanoarchitectures. The designed scattering potential landscapes can be described with semiempirical models, bringing thus the prospect of total control over surface electron confinement and novel quantum states within reach., I. P.-Z., J. L.-C., and J. E. O. acknowledge financial support from the Spanish Ministry of Science and Innovation (MICINN) and the Agencia Estatal de Investigacion (AEI) (Grants No. PID2019-107338RB-C6-3 and No. PID2019-107338RB-C6-4/AEI/10.13039/501100011033), from the regional Government of Aragon (Grant No. E12-20R) and the Basque Government (Grant No. IT-1255-19), and from the European Regional Development Fund (ERDF) under the program Interreg V-A España-Francia-Andorra (Contract No. EFA 194/16 TNSI). W. A. acknowledges funding from the German Research Foundation (DFG; Heisenberg professorship) and the ERC Consolidator Grant NanoSurfs, and J. V. B. acknowledges support from DFG (BA 3395/2-1), ERC (Advanced Grant MolArt), and the DFG Excellence Cluster Munich Center of Quantum Science and Technology (MCQST).

Recently, mixed honeycomb–kagome lattices featuring metal–organic networks have been theoretically proposed as topological insulator materials capable of hosting nontrivial edge states. This new family of so-called “organic topological insulators” are purely two-dimensional and combine polyaromatic-flat molecules with metal adatoms. However, their experimental validation is still pending given the generalized absence of edge states. Here, we generate one such proposed network on a Cu(111) substrate and study its morphology and electronic structure with the purpose of confirming its topological properties. The structural techniques reveal a practically flawless network that results in a kagome network multi-band observed by angle-resolved photoemission spectroscopy and scanning tunneling spectroscopy. However, at the network island borders we notice the absence of edge states. Bond-resolved imaging of the network exhibits an unexpected structural symmetry alteration that explains such disappearance. This collective lifting of the network symmetry could be more general than initially expected and provide a simple explanation for the recurrent experimental absence of edge states in predicted organic topological insulators., We gratefully acknowledge financial support from the Spanish Ministry of Economy, Industry and Competitiveness (MINECO, Grant No. MAT2016-78293-C6-6-R, MAT2016-78293-C6-4-R and MAT2017-83468-R) and the Ministry of Science and Innovation (MICINN, Grant No. PID2019-107338RB-C6-3 and PID2019-107338RB-C6-4), from the regional Government of Aragon (E12-20R RASMIA project and Formación de Personal Investigador, 2018 grant) and the regional Government of the Basque Country (IT-1255-19), from the “Juan de la Cierva” program, and from the European Regional Development Fund (ERDF) under the program Interreg V-A España-Francia-Andorra (Contract No. EFA194/16 TNSI). C. D. is supported by the Royal Society University Research Fellowship (URF/R1/201158)., We acknowledge support of the publication fee by the CSIC Open Access Publication Support Initiative through its Unit of Information Resources for Research (URICI).

Vicinal surfaces exhibiting arrays of atomic steps are frequently investigated due to their diverse physical-chemical properties and their use as growth templates. However, surfaces featuring steps with a large number of low-coordinated kink-atoms have been widely ignored, despite their higher potential for chemistry and catalysis. Here, the equilibrium structure and the electronic states of vicinal Ag(111) surfaces with densely kinked steps are investigated in a systematic way using a curved crystal. With scanning tunneling microscopy we observe an exceptional structural homogeneity of this class of vicinals, reflected in the smooth probability distribution of terrace sizes at all vicinal angles. This allows us to observe, first, a subtle evolution of the terrace-size distribution as a function of the terrace-width that challenges statistical models of step lattices, and second, lattice fluctuations around resonant modes of surface states. As shown in angle resolved photoemission experiments, surface states undergo stronger scattering by fully-kinked step-edges, which triggers the full depletion of the two-dimensional band at surfaces with relatively small vicinal angles., We acknowledge the financial support from the Spanish Ministry of Economy, Industry and Competitiveness (MINECO, Grant No. MAT2016-78293-C6 and Severo Ochoa No. SEV-2013-0295), the Basque Government (Grant No. IT-621-13), the regional Government of Aragon (RASMIA project), the CERCA Programme/Generalitat de Catalunya, and the European Regional Development Fund (ERDF) under the program Interreg V-A España-Francia-Andorra (Contract No. EFA194/16 TNSI).

On-surface metal-organic nanoporous networks generally refer to adatom coordinated molecular arrays, which are characterized by the presence of well-defined and regular nanopores. These periodic structures constructed using two types of components confine the surface electrons of the substrate within their nanocavities. However, the confining (or scattering) strength that individual building units exhibit is a priori unknown. Here, we study the modification of the substrate’s surface electrons by the interaction with a Cu-coordinated TPyB metal-organic network formed on Cu(111) and disentangle the scattering potentials and confinement properties. By means of STM and angle-resolved photoemission spectroscopy we find almost unperturbed free-electron-like states stemming from the rather weak electron confinement that yields significant coupling between adjacent pores. Electron plane wave expansion simulations match the superlattice induced experimental electronic structure, which features replicating bands and energy renormalization effects. Notably, the electrostatic potential landscape obtained from our ab initio calculations suggests that the molecules are the dominant scattering entities while the coordination metal atoms sandwiched between them act as leaky channels. These metal atom transmission conduits facilitate and enhance the coupling among quantum dots, which are prone to be exploited to engineer the electronic structure of surface electron gases., Financial support is acknowledged from the Spanish Ministry of Economy, Industry and Competitiveness (MINECO, Grants No. MAT2016-78293-C6 and No. FIS2016-75862-P), from the regional Government of Aragon (Grant No. E12-17R), from the Basque Government (Grant No. IT-1255-19), from the European Regional Development Fund (ERDF) under the program Interreg V-A España-Francia-Andorra (Contract No. EFA 194/16 TNSI) and from the Hong Kong RGC 16304016.

We present electronic structure calculations based on a single-parameter plane wave expansion method for basic graphene building blocks, namely n-oligophenylenes and n-oligoacenes, revealing excellent agreement with density-functional theory. When oligophenylene molecules are joined through meta (zigzag) or ortho (chevron) junctions, the resulting molecular dimers and polymers exhibit a semiconducting character. While zigzag dimers of oligoacenes also exhibit gapped electronic structures, their chevron-phase features a sharp metallic band at the Fermi energy. This zero-point-energy state, which transforms into Dirac-like band in chevron polymers, survives at the outer elbows of the dimer irrespective of the molecular length, and has the same origin as reported for the polyacetylene and topologically induced edge states at edge-decorated graphene nanoribbons. These findings assist the engineering of topological electronic states at the molecular level and complement the toolbox of quantum phases in carbon-based nanostructures., JEO acknowledges financial support from the Spanish Ministry of Science and Innovation (Grants PID2019-107338RB-C63) and the Basque Government (Grant IT-1255-19).

Graphene nanoribbons (GNRs) can be synthesized with atomic precision through on-surface chemistry of self-assembled organic precursors on metal surfaces. Here, we examine the growth of seven-armchair GNRs (7-AGNRs) on the Au(16 14 15) vicinal surface, namely, a surface vicinal to Au(111) that features kinked steps. During the thermal activation of the polymerization and cyclodehydrogenation processes that produce the GNRs, the kinked substrate undergoes a strong step-edge reshaping, accompanied by a massive missing-row reconstruction within (111) terraces that aligns GNRs preferentially along two equivalent [11¯ 0] directions. Using angle-resolved photoemission, we are able to detect the occupied frontier band of the 7-AGNR at the center of the first Brillouin zone, as predicted by theoretical calculations. This allows to unambiguously determine the relevant 7-AGNR band properties, namely, energy and effective mass., The authors acknowledge financial support from the Spanish Ministry of Science and Innovation (MAT2016-78293-C6), from the Basque Government (IT-1255-19), from the Spanish National Research Council (CSIC, 2019AEP062), from the European Regional Development Fund (ERDF) under the program Interreg V-A España-Francia-Andorra (contract no. EFA 194/16 TNSI) and from the European Research Council (grant agreement no. 635919).

Determining the scattering potential landscape for two-dimensional superlattices provides key insight into fundamental quantum electron phenomena. Theoretical and semiempirical methods have been extensively used to simulate confinement effects of the two-dimensional electron gas (2DEG) on superlattices with a single scatterer in the form of vicinal surfaces and dislocation networks or isolated structures such as quantum corrals and vacancy islands. However, the complexity of the problem increases when the building blocks (or scatterers) are heterogeneous, as in metal-organic nanoporous networks (MONNs), since additional potentials may come into play. Therefore, the parametrization of the surface potential landscape is often inaccurate, leading to incorrect scattering potentials. Here, we address this issue with a combination of scanning tunneling microscopy/spectroscopy, angle resolved photoemission spectroscopy and Kelvin probe force microscopy measurements together with electron plane-wave expansion simulations on a MONN grown on Cu(111). This experimental-Theory approach, enables us to capture the 2DEG response to the intricate scattering potential landscape, and reveals systematic modeling procedures. Starting from a realistic geometry of the system, we determine the repulsive scattering potentials for both molecules and coordinated metal adatoms, the latter contradicting the established simulation framework. Moreover, we reveal local asymmetries and subtle renormalization effects of the 2DEG that relate to the interaction of the MONN and the underlying substrate., We acknowledge the financial support from the Spanish Ministry of Economy, Industry and Competitiveness (MINECO, Grant No. MAT2016-78293-C6), from the Basque Government (Grant No. IT-1255-19), from the regional Government of Aragon (RASMIA project). Part of this work has been performed at the SOLEIL synchrotron at the CASSIOPEE beamline under proposal 20080787. We acknowledge support by the Deutsche Forschungsgemeinschaft (SFB 1249, TP A2 to LHG). SK acknowledges support by Japan Society for the Promotion of Science (JSPS)KAKENHI Grant Number 15K21765. We also acknowledge funding by the Paul Scherrer Institute, the Physics Department of the University of Basel and the Swiss Nanoscience Institute, the Swiss National Science Foundation (Grants # 200020_162512, 206021_144991, 206021_121461) and the Swiss Commission for Technology and Innovation (CTI, 16 465.1 PFNM-NM).

Theoretical progress in graphene physics has largely relied on the application of a simple nearest-neighbor tight-binding model capable of predicting many of the electronic properties of this material. However, important features that include electron-hole asymmetry and the detailed electronic bands of basic graphene nanostructures (e.g., nanoribbons with different edge terminations) are beyond the capability of such a simple model. Here we show that a similarly simple plane-wave solution for the one-electron states of an atom-based two-dimensional potential landscape, defined by a single fitting parameter (the scattering potential), performs better than the standard tight-binding model, and levels to density-functional theory in correctly reproducing the detailed π-band structure of a variety of graphene nanostructures. In particular, our approach identifies the three hierarchies of nonmetallic armchair nanoribbons, as well as the doubly-degenerate flat bands of free-standing zigzag nanoribbons with their energy splitting produced by symmetry breaking. The present simple plane-wave approach holds great potential for gaining insight into the electronic states and electro-optical properties of graphene nanostructures and other two-dimensional materials with intact or gapped Dirac-like dispersions., This work has been supported in part by the Spanish MINECO (Grants No. MAT2014-59096-P, No. MAT2016-78293-C6, No. MAT-2017-88374-P, No. MAT2017-88492-R, and No. SEV2015-0522), the Basque Government (Grant No. IT-1255-19), the European Research Council (Advanced Grant No. 789104-eNANO), the European Commission (Graphene Flagship 696656), the Catalan CERCA Program, Fundació Privada Cellex, and AGAUR (Grant No. 2017 SGR 1651).

Quantum dot arrays in the form of molecular nanoporous networks are renowned for modifying the electronic surface properties through quantum confinement. Here we show that, compared to the pristine surface state, the band bottom of the confined states can exhibit downward shifts accompanied by a lowering of the effective masses simultaneous to the appearance of tiny gaps at the Brillouin zone boundaries. We observed these effects by angle resolved photoemission for two self-Assembled homothetic (scalable) Co-coordinated metal-organic networks. Complementary scanning tunneling spectroscopy measurements confirmed these findings. Electron plane wave expansion simulations and density functional theory calculations provide insight into the nature of this phenomenon, which we assign to metal-organic overlayer-substrate interactions in the form of adatom-substrate hybridization. To date, the absence of the experimental band structure resulting from single metal adatom coordinated nanoporous networks has precluded the observation of the significant surface state renormalization reported here, which we infer to be general for low interacting and well-defined adatom arrays., We acknowledge Prof. J. García de Abajo for providing the EPWE code and the financial support from the Spanish Ministry of Economy, Industry and Competitiveness (MINECO, Grant No. MAT2016-78293-C6 and FIS2016-75862-P), from the Basque Government (Grant No. IT-1255-19 and IT-756-13), from the Regional Government of Aragon (RASMIA project), from the European Regional Development Fund (ERDF) under the program Interreg V-A España-Francia-Andorra (Contract No. EFA 194/16 TNSI) and from the European Research Council (ERC-2012-StG 307760-SURFPRO)., We acknowledge support by the CSIC Open Access Publication Initiative through its Unit of Information Resources for Research (URICI).

The high reactivity of magnetic substrates toward molecular overlayers has so far inhibited the realization of more sophisticated on-surface reactions, thereby depriving these interfaces of a significant class of chemically tailored organics such as graphene nanoribbons, oligonuclear spin-chains, and metal-organic networks. Here, we present a multitechnique characterization of the polymerization of 4,4″-dibromo-p-terphenyl precursors into ordered poly(p-phenylene) arrays on top of the bimetallic GdAu surface alloy. The activation temperatures for bromine scission and subsequent homocoupling of molecular precursors were followed by temperature-dependent X-ray photoelectron spectroscopy. The structural characterizations of supramolecular and polymeric phases, performed by low-energy electron diffraction and scanning tunneling microscopy, establish an extraordinary degree of order extending into the mesoscale. Taking advantage of the high homogeneity, the electronic structure of the valence band was determined with angle-resolved photoemission spectroscopy. Importantly, the transition of localized molecular orbitals into a highly dispersive π-band, the fingerprint of successful polymerization, was observed while leaving all surface-related bands intact. Moreover, ferromagnetic ordering in the GdAu alloy was demonstrated for all phases by X-ray absorption spectroscopy. The transfer of well-established in situ methods for growing covalently bonded macromolecules with atomic precision onto magnetic rare-earth alloys is an important step toward toward studying and controlling intrinsic carbon- and rare-earth-based magnetism., We acknowledge funding from the Spanish MINECO under contract Nos. MAT2013-46593-C6-4-P and MAT2016-78293-C6-5-R as well as the Basque Government Grants IT621-13 and IT-756-13.

A combined scanning tunneling microscopy, x-ray photoelectron spectroscopy, angle-resolved photoemission spectroscopy, and density functional theory study of graphene on a Fe-Ir(111) alloy with variable Ir concentration is presented. Starting from an intercalated Fe layer between the graphene and Ir(111) surface we find that graphene-substrate interaction can be fine-tuned by Fe-Ir alloying at the interface. When a critical Ir-concentration close to 0.25 is reached in the Fe layer, the Dirac cone of graphene is largely restored and can thereafter be tuned across the Fermi level by further increasing the Ir content. Indeed, our study reveals an abrupt transition between a chemisorbed phase at small Ir concentrations and a physisorbed phase above the critical concentration. The latter phase is highly reminiscent of the graphene on the clean Ir(111) surface. Furthermore, the transition is accompanied by an inversion of the graphene's induced magnetization due to the coupling with the Fe atoms from antiferromagnetic when chemisorbed to weakly ferromagnetic in the physisorption regime, with spin polarizations whose magnitude may be tuned with the amount of Fe content., This work has been funded by the Spanish MINECO under contract Nos. FIS2013-48286-C2-1-P, MAT2013-47878-C2-R, MAT2015-66888-C3-1R, and MAT2013-46593-C6-4-P as well as the Basque Government Grants IT621-13 and IT756-13.

Resumen del trabajo presentado a la 13th European Conference on Surface Crystallography and Dynamics, celebrada en Donostia-San Sebastián (España) del 19 al 21 de junio de 2017., Quantum dot (QD) arrays on surfaces, generated through molecular self-assembly processes, have so far provided researchers with a vast playground to study the electronic properties of new and exotic 2D materials in ultra-high-vacuum (UHV) conditions. By selecting the proper molecular constituents (tectons) and substrate, long-range ordered, periodic and robust nanoporous networks have been achieved, ranging from hydrogen-bonded to metal-organic structures. Not only do they stand out as ideal templates for nanopatterning, but also as adequate candidates for studying fundamental physical phenomena such as confinement through the scattering of two-dimensional electron gases (2DEGs). Indeed, confinement tunability has already been accomplished by varying the pore (i.e. quantum dot) dimensions, geometrical shape and molecule substrate interactions. In addition, inter-dot coupling has been shown by photoemission through the generation of new dispersive bands that can be modulated through thermodynamics and the condensation of guest elements (Xe atoms). To date, the modification of 2DEGs through inter-dot barrier width variations has not been experimentally demonstrated. Herein, sustained upon a combination of local scanning probes (STM/STS/AFM), angle resolved photoemission spectroscopy (ARPES) and extended model calculations, we show that we can precisely engineer the inter-dot barrier width by substitution of a single atom in a haloaromatic compound. As a result, we tune the confinement properties at each nanopore affecting the degree of QD intercoupling both on bulk and thin Ag films alike. These findings pave the way to reach full control over 2DEGs with the prospect of becoming key for future electronic devices.

Two-dimensional organic and metal-organic nanoporous networks can scatter surface electrons, leading to their partial localization. Such quantum states are related to intrinsic surface states of the substrate material. We further corroborate this relation by studying the thermally induced energy shifts of the electronic band stemming from coupled quantum states hosted in a metal-organic array formed by a perylene derivative on Cu(111). We observe by angle-resolved photoemission spectroscopy (ARPES), that both, the Shockley and the partially localized states, shift by the same amount to higher binding energies upon decreasing the sample temperature, providing evidence of their common origin. Our experimental approach and results further support the use of surface states for modelling these systems, which are expected to provide new insight into the physics concerning partially confined electronic states: scattering processes, potential barrier strengths, excited state lifetimes or the influence of guest molecules., We acknowledge financial support from the Spanish Ministry of Economy (grant MAT2013-46593-C6-4-P), the Basque Government (grant IT621-13), the Spanish Research Council (CSIC-201560I022), the Swiss Nanoscience Institute (SNI), Swiss National Science Foundation (grants Nos. 200020-149713, 206021-121461), the Netherlands Organization for Scientific Research (NWO Vidi grant No. 700.10.424), the European Research Council (ERC-2012-StG 307760-SURFPRO) and the Paul Scherrer Institute.

Communication.-- et al., A 2D array of electronically coupled quantum boxes is fabricated by means of on-surface self-assembly assuring ultimate precision of each box. The quantum states embedded in the boxes are configured by adsorbates, whose occupancy is controlled with atomic precision. The electronic interbox coupling can be maintained or significantly reduced by proper arrangement of empty and filled boxes., The authors would like to acknowledge financial support from the Swiss Nanoscience Institute (SNI), Swiss National Science Foundation (Grants Nos. 200020-149713 and 206021-121461), the Spanish Ministry of Economy (Grant No. MAT2013-46593-C6-4-P), the Basque Government (Grant No. IT621-13), the São Paulo Research Foundation (Grant No. 2013/04855-0), Swiss Government Excellence Scholarship Program, Netherlands Organization for Scientific Research NWO (Chemical Sciences, VIDI-Grant No. 700.10.424), the European Research Council (ERC-2012-StG 307760-SURFPRO), University of Basel, University of Heidelberg, Linköping University, University of Groningen, Paul Scherrer Institute, and the Japan Science and Technology Agency (JST) “Precursory Research for Embryonic Science and Technology (PRESTO)” for a project of “Molecular technology and creation of new function.”