Molecular nanoarchitectonics: unification of nanotechnology and molecular/materials science

• Katsuhiko Ariga

Beilstein J. Nanotechnol. 2023, 14, 434–453, doi:10.3762/bjnano.14.35

• molecular structures. Kawai et al. reported that local probe chemistry on an ultrathin NaCl film formed on a Cu(111) surface at 4.3 K led to the conversion of 6,13-dibromopentaleno[1,2-b:4,5-b′]dinaphthalene to a single Sondheimer–Wong diyne (Figure 3) [114]. The structures of the precursor, two

• polydiacetylene nanowires at designated locations on a solid surface. Figure 2 was adapted with permission from [112], Copyright 2014 American Chemical Society. This content is not subject to CC-BY-4.0. Local probe chemistry on an ultra-thin NaCl film formed on a Cu(111) surface for the synthesis of 6,13

Topographic signatures and manipulations of Fe atoms, CO molecules and NaCl islands on superconducting Pb(111)

• Carl Drechsel,
• Philipp D’Astolfo,
• Jung-Ching Liu,
• Thilo Glatzel,
• Rémy Pawlak and
• Ernst Meyer

Beilstein J. Nanotechnol. 2022, 13, 1–9, doi:10.3762/bjnano.13.1

• Cu(111) [62]. Occasionally, even a trilayer phase appears within the NaCl bilayer (Figure 3a and Figure 3b). Note also that dark protrusions originating from trapped Ar atoms are still visible through the NaCl island by STM as well as point defects. We do not exclude that these might be Cl vacancies

• image in Figure 4c. The darkest features are spaced by 0.35 Å in agreement with the lattice parameters of Pb(111) and likely correspond to hollow sites of the fcc structure of Pb(111). Indeed, we think that Fe atoms are preferentially adsorbed at these sites similar to Fe on Cu(111) [72]. Using this

• trimer (Fe3). Compared to the heights of Fe1 and Fe2, the height of Fe3 is about h3 = 1.7 Å. This evolution of STM apparent heights as a function of number of atoms in small Fe clusters is in good agreement with a similar study of Fe clusters on Cu(111) [72]. Conclusion Our results report on the

Molecular assemblies on surfaces: towards physical and electronic decoupling of organic molecules

• Sabine Maier and
• Meike Stöhr

Beilstein J. Nanotechnol. 2021, 12, 950–956, doi:10.3762/bjnano.12.71

• example of (1S)-camphor on Cu(111) [72]. Such computational tools become relevant for molecules with bulky spacer groups since they are very valuable for predicting and interpreting the structural and conformational properties as well as the decoupling of such molecules on surfaces. With an appropriate

• otherwise only achieved for multilayers on the bare Ni. On hBN/Cu(111), Zimmermann et al. [87] could visualize the molecular orbitals of pyrene derivatives by STM at the submolecular level, while Brülke et al. [88] measured the fluorescence of monolayer perylenetetracarboxylic dianhydride (PTCDA), which is

• quenched on bare Cu(111) and would require three molecular decoupling layers to be probed on Cu(111). In all three studies using hBN, ordered molecular films were observed. The decoupling even allowed for the formation of complex self-assemblies such as kagome lattices by tuning the number and position of

Local stiffness and work function variations of hexagonal boron nitride on Cu(111)

• Abhishek Grewal,
• Yuqi Wang,
• Matthias Münks,
• Klaus Kern and
• Markus Ternes

Beilstein J. Nanotechnol. 2021, 12, 559–565, doi:10.3762/bjnano.12.46

• materials at the nanoscale. In this work, we study hexagonal boron nitride (h-BN), an atomically thin 2D layer, that is van der Waals-coupled to a Cu(111) surface. The system is of interest as a decoupling layer for functional 2D heterostructures due to the preservation of the h-BN bandgap and as a template

• for atomic and molecular adsorbates owing to its local electronic trapping potential due to the in-plane electric field. We obtain work function (Φ) variations on the h-BN/Cu(111) superstructure of the order of 100 meV using two independent methods, namely the shift of field emission resonances and

• 9.4 ± 0.9 N·m−1, which is one order of magnitude higher than the one obtained for h-BN/Rh(111). Using constant force maps we are able to derive height profiles of h-BN/Cu(111) showing that the system has a corrugation of 0.6 ± 0.2 Å, which helps to demystify the discussion around the flatness of the h

Determining amplitude and tilt of a lateral force microscopy sensor

• Oliver Gretz,
• Alfred J. Weymouth,
• Thomas Holzmann,
• Korbinian Pürckhauer and
• Franz J. Giessibl

Beilstein J. Nanotechnol. 2021, 12, 517–524, doi:10.3762/bjnano.12.42

• , Germany) operating in ultra-high vacuum at 5.6 K equipped with a qPlus sensor [25]. The sensor was equipped with an etched tungsten tip, which was repeatedly poked into a Cu(111) surface to generate well-defined tip apex configurations. Cu(111) was cleaned by standard sputtering and annealing cycles

• single iron adatom on Cu(111) taken with a metal tip. The similarity with the simulated curves shown in Figure 3 can be seen. However, small discrepancies are visible. The reason for the discrepancies are Cu(111) surface states and nearby CO molecules, which were captured in the data. The inset in Figure

•  4b shows an STM image of a single iron adatom [26]. The red solid curve in Figure 4c shows the current profile ⟨I⟩ along a line in the x-direction over a single iron adatom on Cu(111) with tip oscillation. The blue dashed curve is the fitted , yielding A = 1050 pm ± 2% and θ = 1.59° ± 2%. The

Reconstruction of a 2D layer of KBr on Ir(111) and electromechanical alteration by graphene

• Zhao Liu,
• Antoine Hinaut,
• Stefan Peeters,
• Sebastian Scherb,
• Ernst Meyer,
• Maria Clelia Righi and
• Thilo Glatzel

Beilstein J. Nanotechnol. 2021, 12, 432–439, doi:10.3762/bjnano.12.35

• intercalation of a third material between a substrate and a 2D layer can be applied to tune the physical properties [13][14][15][16][17]. Schulzendorf et al. reported the electrical decoupling of graphene islands by the intercalation of single layers of KBr between the Cu(111) metal substrate and graphene

• contrast, on hexagonal (111) oriented metal surfaces, alkali halides were reported to arrange in cubic islands [31][32][33]. Sometimes, they exhibit a moiré pattern, for example, as a result of the incommensurate growth in the system of NaCl/Cu(111) [34]. Furthermore, considering the interface of alkali

• a new surface structure, different from the one on other metal substrates such as Cu(111) [42]. Now, the question arises if this structure is a moiré lattice (lateral relaxation) induced by an alternating strength of interaction forces or a new reconstruction of the KBr layer. To search for this

The influence of an interfacial hBN layer on the fluorescence of an organic molecule

• Christine Brülke,
• Oliver Bauer and
• Moritz M. Sokolowski

Beilstein J. Nanotechnol. 2020, 11, 1663–1684, doi:10.3762/bjnano.11.149

• organic molecule 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) from the supporting Cu(111) surface by Raman and fluorescence (FL) spectroscopy. The Raman fingerprint-type spectrum of PTCDA served as a monitor for the presence of molecules on the surface. Several broad and weak FL lines between

• 18,150 and 18,450 cm−1 can be detected, already from the first monolayer onward. In contrast, FL from PTCDA on a bare Cu(111) surface is present only from the second PTCDA layer onward. Hence, a single layer of hBN decouples PTCDA from the metal substrate to an extent that a weak radiative FL decay of

• system of this work, namely, 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) on a layer of hBN on Cu(111). Here, we consider an S1 excitation which involves mainly a HOMO/LUMO (highest occupied and lowest unoccupied molecular orbital) electronic excitation. Rapid CT leads to a delocalization of the

PTCDA adsorption on CaF₂ thin films

• Philipp Rahe

Beilstein J. Nanotechnol. 2020, 11, 1615–1622, doi:10.3762/bjnano.11.144

• is also noteworthy that PTCDA on bulk NaCl(001) surfaces shows long-range order with a dewetting transition at a certain coverage [18], while experiments using NaCl thin films on Cu(111) revealed an absence of long-range order with molecules rather bound to step edges [22]. Explanations for this

• partially KBr-covered Ag(111) surfaces [24] as well as for cyanoporphyrin molecules on KBr-covered Cu(111) surfaces [26]. Here, the understanding of molecular adsorption on insulating thin films is extended by studying an insulator-on-semiconductor system, namely CaF2 thin films grown on Si(111) surfaces

Detecting stable adsorbates of (1S)-camphor on Cu(111) with Bayesian optimization

• Jari Järvi,
• Patrick Rinke and
• Milica Todorović

Beilstein J. Nanotechnol. 2020, 11, 1577–1589, doi:10.3762/bjnano.11.140

• Bayesian Optimization Structure Search (BOSS) method as an efficient solution for identifying the structure of non-planar adsorbates. We apply BOSS with density-functional theory simulations to detect the stable adsorbate structures of (1S)-camphor on the Cu(111) surface. We identify the optimal structure

• among eight unique types of stable adsorbates, in which camphor chemisorbs via oxygen (global minimum) or physisorbs via hydrocarbons to the Cu(111) surface. This study demonstrates that new cross-disciplinary tools, such as BOSS, facilitate the description of complex surface structures and their

• properties, and ultimately allow us to tune the functionality of advanced materials. Keywords: Bayesian optimization; camphor; Cu(111); density-functional theory; electronic structure; organic surface adsorbates; physical chemistry; structure search; surface science; Introduction Current frontier

Adsorption and self-assembly of porphyrins on ultrathin CoO films on Ir(100)

• Feifei Xiang,
• Tobias Schmitt,
• Marco Raschmann and
• M. Alexander Schneider

Beilstein J. Nanotechnol. 2020, 11, 1516–1524, doi:10.3762/bjnano.11.134

• be detected (Figure 3b). This latter observation remains true for larger coverages at which the size of such agglomerates is increased. The situation for 2 is comparable to adsorption properties observed on Cu(111) when metal-organic coordination is not activated [10]. However, different to Cu(111

• homogeneous contrast develops in Figure 4d. Such compact assemblies were previously observed for the case of the non-metalated 2H-DPP compound on Ag(110) [24] and on Au(111) [22], but, for example, not on Cu(111) [23]. For the assembly on 1BL CoO, the distance between the phenyl rings is a little larger than

• into a state of low-energy at an appropriate bonding distance. This is, for example, observed at low coverage of 2H-DPP on Cu(111) [23]. When, as it appears here, the diffusion and the rotational barrier are of equal magnitude, the intermolecular forces cannot exert their directional influence on the

Controlling the electronic and physical coupling on dielectric thin films

• Philipp Hurdax,
• Michael Hollerer,
• Larissa Egger,
• Georg Koller,
• Xiaosheng Yang,
• Anja Haags,
• Serguei Soubatch,
• Frank Stefan Tautz,
• Mathias Richter,
• Alexander Gottwald,
• Peter Puschnig,
• Martin Sterrer and
• Michael G. Ramsey

Beilstein J. Nanotechnol. 2020, 11, 1492–1503, doi:10.3762/bjnano.11.132

• : decoupling; integer charge transfer; organic films; para-sexiphenyl; thin dielectric film; Introduction Since the first scanning tunneling microscope (STM) imaging of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of pentacene (5A) on NaCl/Cu(111) was

Self-assembly and spectroscopic fingerprints of photoactive pyrenyl tectons on hBN/Cu(111)

• Domenik M. Zimmermann,
• Knud Seufert,
• Luka Ðorđević,
• Tobias Hoh,
• Sushobhan Joshi,
• Tomas Marangoni,
• Davide Bonifazi and
• Willi Auwärter

Beilstein J. Nanotechnol. 2020, 11, 1470–1483, doi:10.3762/bjnano.11.130

• . Scanning tunneling microscopy (STM) and spectroscopy (STS) measurements of the pyrene derivatives adsorbed on a Cu(111)-supported hexagonal boron nitride (hBN) decoupling layer provided access to spatially and energetically resolved molecular electronic states. We demonstrate that the pyrene electronic gap

• as such spacer layers [18] and can promote site-dependent decoupling and adsorption [19][20], yielding access to optical transitions [21] as well as allowing for orbital-resolved STM imaging [19][21][22][23]. For instance, hBN/Cu(111) [24][25][26][27] features a work function template with a moiré

• superstructure: Depending on the registry of the layer and substrate atoms, the surface is divided in areas of low and high local work function, denoted as “pores” and “wires”, respectively [28][29][30][31]. In recent years, our group and others used hBN/Cu(111) to guide the self-assembly of porphyrins [28][32

Impact of fluorination on interface energetics and growth of pentacene on Ag(111)

• Qi Wang,
• Meng-Ting Chen,
• Antoni Franco-Cañellas,
• Bin Shen,
• Thomas Geiger,
• Holger F. Bettinger,
• Frank Schreiber,
• Ingo Salzmann,
• Alexander Gerlach and
• Steffen Duhm

Beilstein J. Nanotechnol. 2020, 11, 1361–1370, doi:10.3762/bjnano.11.120

• physisorptive [29][53]. On Cu(111), PFP shows a behavior close to physisorption [9], although the coupling strength might be slightly stronger than with Au(111) [54]. PEN on Cu(111), however, is strongly chemisorbed, involving a partial filling of the former lowest unoccupied molecular orbital (LUMO) by a

• charge transfer from the substrate [9][28]. This can be explained by the repulsive interaction of the fluorine atoms with the substrate, which leads to much larger vertical adsorption heights of PFP compared to PEN in monolayers on Cu(111) [9]. Ag(111) represents an intermediate case [55] with weak

• fluorinated PEN, namely 2,3,9,10-tetrafluoropentacene (F4PEN) [46][60][61]. F4PEN physisorbs on Au(111) [62] and chemisorbs on Cu(111), involving interfacial charge transfer and strong molecular distortions [63]. Here, we investigated the coupling with Ag(111) as we expected this to be an interesting

Hybridization vs decoupling: influence of an h-BN interlayer on the physical properties of a lander-type molecule on Ni(111)

• Maximilian Schaal,
• Takumi Aihara,
• Marco Gruenewald,
• Felix Otto,
• Jari Domke,
• Roman Forker,
• Hiroyuki Yoshida and
• Torsten Fritz

Beilstein J. Nanotechnol. 2020, 11, 1168–1177, doi:10.3762/bjnano.11.101

• on h-BN/Cu(111) were found recently [11][12]. This raises the question under which specific conditions an h-BN monolayer is sufficient to efficiently decouple organic molecules. Until now only a few publications exist which are concerned with this issue [13][14][15][16]. In this work we report on the

Scanning tunneling microscopy and spectroscopy of rubrene on clean and graphene-covered metal surfaces

• Karl Rothe,
• Alexander Mehler,
• Nicolas Néel and
• Jörg Kröger

Beilstein J. Nanotechnol. 2020, 11, 1157–1167, doi:10.3762/bjnano.11.100

• phthalocyanine molecules on graphene-covered SiO2/Si samples [5] as well as on h-BN-covered Ir(111) [6], of conjugated oligohenylenes on h-BN-covered Cu(111) [7], of manganese phthalocyanine on h-BN-covered Rh(111) [8], and of 5,10,15,20-tetraphenylbisbenz[5,6]indendo[1,2,3-cd:1′,2′,3′-lm]perylene on graphene

Adsorption behavior of tin phthalocyanine onto the (110) face of rutile TiO₂

• Lukasz Bodek,
• Mads Engelund,
• Aleksandra Cebrat and
• Bartosz Such

Beilstein J. Nanotechnol. 2020, 11, 821–828, doi:10.3762/bjnano.11.67

• between Sn-up and Sn-down was also reported on Cu(111) and Ag(100), while this reaction did not occur on Au(111) and Au(110) surfaces [28]. On the Ag(111) surface, within the first layer, Sn-up molecules were irreversibly switched to the down position, while on InAs(111), the molecules could be switched

Polymorphic self-assembly of pyrazine-based tectons at the solution–solid interface

• Achintya Jana,
• Puneet Mishra and
• Neeladri Das

Beilstein J. Nanotechnol. 2019, 10, 494–499, doi:10.3762/bjnano.10.50

• adsorbed on Cu(111) [16]. No such distortion of the molecular symmetry was observed when these molecules were adsorbed on Ag(111) substrate [15] or at the solution–solid interface [23], where the molecule–substrate interaction is weaker than that on Cu(111). A weak molecule–substrate interaction is

Apparent tunneling barrier height and local work function of atomic arrays

• Neda Noei,
• Alexander Weismann and
• Richard Berndt

Beilstein J. Nanotechnol. 2018, 9, 3048–3052, doi:10.3762/bjnano.9.283

• operated at 4.5 K. Cu(111) surfaces were cleaned by Ar+ sputter/anneal cycles. W tips were electrochemically etched from polycrystalline wire. After sputtering, they were further prepared in situ by indenting them into the Cu(111) substrate. Because of this procedure, the tips were presumably covered with

• topographs and from a characteristic signature in differential conductance (dI/dV) spectra. As first reported by Fölsch et al., short single-atom Cu chains on Cu(111) exhibit an unoccupied resonance at 1.5 eV above the Fermi energy EF [36]. Closely related data including the limit of very long chains were

• is of the order of 1 eV. This complicates the relation between the local sample work function Φ and the measured Φapp. The shape of the tip also influences the degree of confinement and presumably contributes to the scatter of Φapp observed with different tips. STM images of a Cu(111) surface with

Recent highlights in nanoscale and mesoscale friction

• Andrea Vanossi,
• Dirk Dietzel,
• Andre Schirmeisen,
• Ernst Meyer,
• Rémy Pawlak,
• Thilo Glatzel,
• Marcin Kisiel,
• Shigeki Kawai and
• Nicola Manini

Beilstein J. Nanotechnol. 2018, 9, 1995–2014, doi:10.3762/bjnano.9.190

• [47], as discussed in Section “Controlled nanomovements” (see Figure 2). Pawlak et al. investigated the sliding of a single molecule on a Cu(111) surface in order to shed light on the interplay between intra-molecular mechanics and friction [183]. The experiment was realized by attaching a single

Heterostuctures of 4-(chloromethyl)phenyltrichlorosilane and 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine prepared on Si(111) using particle lithography: Nanoscale characterization of the main steps of nanopatterning

• Phillip C. Chambers and
• Jayne C. Garno

Beilstein J. Nanotechnol. 2018, 9, 1211–1219, doi:10.3762/bjnano.9.112

• ], catalysis [10] and electronic measurements [11][12][13]. Investigations of porphyrins at interfaces have focused on elucidation of magnetic, photonic and electronic properties as well as the manner in which the molecules assemble on a surface. The adsorption of free-base tetraphenylporphyrin on Cu(111) was

• studied with scanning tunneling microscopy (STM) to evaluate the surface conformation and molecular geometry [14]. Individual molecules of nonplanar freebase and copper-metallated tetraphenyl porphyrins adsorbed on Cu(111) were investigated using frequency modulated noncontact AFM to resolve subtle

• with a surface orientation defined by the substituents [20]. The self-assembly of manganese meso-tetra(4-pyridyl)porphyrin on Cu(111) was studied using low temperature scanning tunneling microscopy (STM) and atomic force microscopy (AFM) to resolve molecular structures by Chen et al. [21]. A

Adsorption of iron tetraphenylporphyrin on (111) surfaces of coinage metals: a density functional theory study

• Hao Tang,
• Nathalie Tarrat,
• Véronique Langlais and
• Yongfeng Wang

Beilstein J. Nanotechnol. 2017, 8, 2484–2491, doi:10.3762/bjnano.8.248

• The adsorption of the iron tetraphenylporphyrin (FeTPP) molecule in its deckchair conformation was investigated on Au(111), Ag(111) and Cu(111) surfaces by performing spin-polarized density functional theory (DFT) calculations taking into account both van der Waals (vdW) interaction and on-site

• agreement with the experimental one (5.35 eV) [23]. After the adsorption, the work function was reduced to 4.19 eV. This value is consistent with that measured on copper phthalocyanine (CuPc) adsorbed on Au(111) [24]. Adsorption on Ag(111) and Cu(111) surfaces It is well known for large organic molecules

• sites of Ag(111) and Cu(111) surfaces (Figure 8). The adsorption energy for HS FeTPP on Ag(111) is −4.99 ± 0.01 eV with a molecule–surface distance of dFeTPP-Ag(111) = 3.06 ± 0.01 Å and an Fe–surface distance of dFe-Ag(111) = 2.82 ± 0.01 Å. On Cu(111), the adsorption energy of HS FeTPP is −4.85 ± 0.02

Robust procedure for creating and characterizing the atomic structure of scanning tunneling microscope tips

• Sumit Tewari,
• Koen M. Bastiaans,
• Milan P. Allan and
• Jan M. van Ruitenbeek

Beilstein J. Nanotechnol. 2017, 8, 2389–2395, doi:10.3762/bjnano.8.238

• structure of the tip apex behind the apex atom. Some studies have been carried out to determine the angular orbital symmetry [21][22] of the front atom of the tip apex by making force gradient images of a CO molecule over a Cu(111) substrate. The images are made with a tungsten tip in non-contact AFM

Ester formation at the liquid–solid interface

• Nguyen T. N. Ha,
• Thiruvancheril G. Gopakumar,
• Nguyen D. C. Yen,
• Carola Mende,
• Lars Smykalla,
• Maik Schlesinger,
• Roy Buschbeck,
• Tobias Rüffer,
• Heinrich Lang,
• Michael Mehring and
• Michael Hietschold

Beilstein J. Nanotechnol. 2017, 8, 2139–2150, doi:10.3762/bjnano.8.213

• reaction, etc. have been explored on surfaces [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. In the publication by Hla et al. [1] the reaction of two single iodobenzene molecules towards one biphenyl molecule (an Ullmann reaction) on the edge of a monoatomic step of a Cu(111) substrate surface has been

• -octabromo-5,10,15,20-tetraphenylporphyrin (CuTPPBr8) at an Au(111) substrate [2] or the polymerization of 1,3,6,8-tetrabromopyrene on Cu(111) and Au(111) substrates [3]. Characteristic for all these studies is that they are performed at an almost ideal monocrystalline surface in ultra-high vacuum (UHV). On

Coexistence of strongly buckled germanene phases on Al(111)

• Weimin Wang and
• Roger I. G. Uhrberg

Beilstein J. Nanotechnol. 2017, 8, 1946–1951, doi:10.3762/bjnano.8.195

• bilayer germanene on Cu(111) at room temperature. Scanning tunneling spectroscopy showed a “V” shaped density of states, which was also observed by Zhang et al. [12], who synthesized germanene on MoS2 at room temperature. Al(111) was chosen as a substrate to deposit germanene by Derivaz et al. [13] with

Adsorption and electronic properties of pentacene on thin dielectric decoupling layers

• Sebastian Koslowski,
• Daniel Rosenblatt,
• Alexander Kabakchiev,
• Klaus Kuhnke,
• Klaus Kern and
• Uta Schlickum

Beilstein J. Nanotechnol. 2017, 8, 1388–1395, doi:10.3762/bjnano.8.140

• metal [7]. For example, it has been shown that NaCl with a thickness of merely one to three atomic layers grown on a Cu(111) surface provides sufficient electronic decoupling between pentacene molecules and the metal surface [6]. The influence of the inert NaCl layer on the molecules is very small, as

• of the molecular position d and the dielectric constant of a single sheet of h-BN. Similar STS measurements of pentacene were carried out on KCl/Au(111), KCl/Cu(111) and KCl/(Cu110). The resulting STS data are depicted in Figure 7. The HOMO–LUMO gap can be used as a measure of the efficiency of an

• were generated by thermal evaporation of KCl at 653 K for 20 min. During this process, the substrates were kept at room temperature. The metal substrates (Au(111), Cu(111), Cu(110)) were cleaned by alternating sequences of Ar-ion bombardment and annealing at 843 K. The annealing temperature was reduced