Molecular nanoarchitectonics: unification of nanotechnology and molecular/materials science

• Katsuhiko Ariga

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

• and on-surface synthesis. As shown in these examples, nanotechnology has made great contributions to organic chemistry, and it is now possible to observe reaction processes at molecular resolution. In addition, organic synthesis can be freely controlled by manipulation at the molecular level using

Two dynamic modes to streamline challenging atomic force microscopy measurements

• Alexei G. Temiryazev,
• Andrey V. Krayev and
• Marina P. Temiryazeva

Beilstein J. Nanotechnol. 2021, 12, 1226–1236, doi:10.3762/bjnano.12.90

• formalized choice of the imaging parameters in these modes allows addressing a wide range of formerly challenging tasks – from scanning rough samples with high aspect ratio features to molecular resolution imaging. Keywords: atomic force microscopy; dissipation mode; scanning probe microscopy; vertical mode

• for scanning a large rough area with a probe oscillating at a low amplitude. In contrast, the use of ultrasharp probes allows for performing extremely high-resolution imaging (down to molecular resolution) when scanning small and relatively flat areas. Thus, with the same probe, we can pre-scan a

Influence of electrospray deposition on C₆₀ molecular assemblies

• Antoine Hinaut,
• Sebastian Scherb,
• Sara Freund,
• Zhao Liu,
• Thilo Glatzel and
• Ernst Meyer

Beilstein J. Nanotechnol. 2021, 12, 552–558, doi:10.3762/bjnano.12.45

• = 1.079 MHz, A2 = 800 pm, Δf2 = −30 Hz; (c, e) f1 = 152 kHz, A1 = 8 nm, Δf1 = −8 Hz. The crystal lattice orientation is shown in (b). Scale bar: (a–c) 100 nm, (d) 2 nm, (e) 10 nm. C60 on a NiO(001) surface. (a) Large scale topography nc-AFM image after TE; inset: zoom on an island with molecular

• resolution. (b) Topography nc-AFM image after HV-ESD. Parameters: (a) f1 = 169 kHz, A1 = 8 nm, Δf1 = −5 Hz; (b) f2 = 1.057 MHz, A2 = 800 pm, Δf2 = −10 Hz. Scale bar: (a, b) 50 nm, inset 2 nm. Supporting Information Supporting Information features additional images of the influence of HV-ESD on surfaces and

Protruding hydrogen atoms as markers for the molecular orientation of a metallocene

• Linda Laflör,
• Michael Reichling and
• Philipp Rahe

Beilstein J. Nanotechnol. 2020, 11, 1432–1438, doi:10.3762/bjnano.11.127

• -molecular resolution imaging at 77 K [37][38] and 300 K [39]. Due to the predominant repulsive interactions with the chemically rather inert hydrogen atoms, we speculate that the chemical identity of the tip is therefore of secondary importance. Still, the tip has to be sharp enough to allow for resolving

Three-dimensional solvation structure of ethanol on carbonate minerals

• Hagen Söngen,
• Ygor Morais Jaques,
• Peter Spijker,
• Christoph Marutschke,
• Stefanie Klassen,
• Ilka Hermes,
• Ralf Bechstein,
• Lidija Zivanovic,
• John Tracey,
• Adam S. Foster and
• Angelika Kühnle

Beilstein J. Nanotechnol. 2020, 11, 891–898, doi:10.3762/bjnano.11.74

• surfaces interact with a large variety of organic molecules, which can result in surface restructuring. This process is decisive for the formation of biominerals. With the development of 3D atomic force microscopy (AFM) it is now possible to image solid–liquid interfaces with unprecedented molecular

• resolution. However, the majority of 3D AFM studies have been focused on the arrangement of water at carbonate surfaces. Here, we present an analysis of the assembly of ethanol – an organic molecule with a single hydroxy group – at the calcite and magnesite (10.4) surfaces by using high-resolution 3D AFM and

Comparing a porphyrin- and a coumarin-based dye adsorbed on NiO(001)

• Sara Freund,
• Antoine Hinaut,
• Nathalie Marinakis,
• Edwin C. Constable,
• Ernst Meyer,
• Catherine E. Housecroft and
• Thilo Glatzel

Beilstein J. Nanotechnol. 2019, 10, 874–881, doi:10.3762/bjnano.10.88

• Kelvin probe force microscopy measurements. Keywords: coumarin; Kelvin probe force microscopy; metal oxide; molecular resolution; nickel oxide (NiO); non-contact atomic force microscopy; porphyrin; Introduction With regard to its use in dye-sensitized solar cells (DSSCs), the wide-bandgap n-type

Mechanical and thermodynamic properties of Aβ₄₂, Aβ₄₀, and α-synuclein fibrils: a coarse-grained method to complement experimental studies

• Adolfo B. Poma,
• Horacio V. Guzman,
• Mai Suan Li and
• Panagiotis E. Theodorakis

Beilstein J. Nanotechnol. 2019, 10, 500–513, doi:10.3762/bjnano.10.51

• be determined during experimental measurements. As a result, big discrepancies are found when comparing Young’s modulus values measured with macroscopic techniques and nanoscopic ones such as AFM. This is because a nanoscopic exploration of biological systems reaches molecular resolution and the

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

• leading to the formation of molecular arrays. In region II, the molecular arrangement exhibits carpet-like striations. The angle between the two length-wise orientations of the molecules in region II is measured to be approximately 70°. As depicted in the STM images with sub-molecular resolution (Figure

• theoretical simulations [24][25][26]. For this purpose, our experimental results with sub-molecular resolution can provide valuable inputs for future theoretical calculations on related molecule–substrate systems. Another possible reason for the observed polymorphism could be attributed to a competition

• the solution–solid interface. (a) Large-scale STM image; Vs = 1.4 V, It = 1 nA. (b) STM image showing two polymorphs separated by a domain boundary indicated by a solid white line. Vs = 0.8 V, It = 400 pA. (c, d) STM images with sub-molecular resolution depicting the molecular packing in the two

Anchoring of a dye precursor on NiO(001) studied by non-contact atomic force microscopy

• Sara Freund,
• Antoine Hinaut,
• Nathalie Marinakis,
• Edwin C. Constable,
• Ernst Meyer,
• Catherine E. Housecroft and
• Thilo Glatzel

Beilstein J. Nanotechnol. 2018, 9, 242–249, doi:10.3762/bjnano.9.26

• (II) oxide (NiO); non-contact atomic force microscopy; p-type semiconductor; sub-molecular resolution; Introduction Inorganic substrates functionalized with organic molecules are nowadays highly regarded materials for emerging hybrid technologies including molecular electronics, photocatalysts or

Patterning of supported gold monolayers via chemical lift-off lithography

• Liane S. Slaughter,
• Kevin M. Cheung,
• Sami Kaappa,
• Huan H. Cao,
• Qing Yang,
• Thomas D. Young,
• Andrew C. Serino,
• Sami Malola,
• Jana M. Olson,
• Stephan Link,
• Hannu Häkkinen,
• Anne M. Andrews and
• Paul S. Weiss

Beilstein J. Nanotechnol. 2017, 8, 2648–2661, doi:10.3762/bjnano.8.265

• measured by electron diffraction [55][56]. At molecular resolution, scanning probe measurements have revealed the rearrangement of Au surface atoms [57][58][59], diffusion and alignment of adatom–adsorbate complexes [50][60], and phase separation of SAMs composed of molecules with different backbones or

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

• adopts a deckchair form (C2h). These conformations have been identified in sub-molecular resolution STM images on a Au(111) surface as shown in the work of N. Lin et al. [16] for the saddle conformation (twofold symmetry) and in the work of Gopakumar et al. [11] for the planar conformation (fourfold

Scaling law to determine peak forces in tapping-mode AFM experiments on finite elastic soft matter systems

• Horacio V. Guzman

Beilstein J. Nanotechnol. 2017, 8, 968–974, doi:10.3762/bjnano.8.98

• -modulation atomic force microscopy (AM-AFM) is the most common method to generate atomic and molecular resolution images of diverse materials in liquid environment [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15]. In AM-AFM (tapping mode) a sharp tip is attached at the end of a microcantilever that

Ordering of Zn-centered porphyrin and phthalocyanine on TiO₂(011): STM studies

• Piotr Olszowski,
• Lukasz Zajac,
• Szymon Godlewski,
• Bartosz Such,
• Rémy Pawlak,
• Antoine Hinaut,
• Res Jöhr,
• Thilo Glatzel,
• Ernst Meyer and
• Marek Szymonski

Beilstein J. Nanotechnol. 2017, 8, 99–107, doi:10.3762/bjnano.8.11

• overlayer on the rutile (011) face clearly indicates molecular resolution achieved at room temperature (see Figure 2) and the linear cross-cuts along [01−1] and [100] directions allow for a precise geometrical characterization of the molecule configuration within the first surface overlayer. Similarly to

• characterized by a balance between strong mutual interaction between the molecules in the upright configuration and a relatively weak coupling to the wetting layer. From the molecular resolution of the image in Figure 3b and the STM images of other ZnPc islands grown on the wetting layer, we know that the

Modelling of ‘sub-atomic’ contrast resulting from back-bonding on Si(111)-7×7

• Adam Sweetman,
• Samuel P. Jarvis and
• Mohammad A. Rashid

Beilstein J. Nanotechnol. 2016, 7, 937–945, doi:10.3762/bjnano.7.85

• obtained during imaging of planar organic molecules [3][4]. An important development in the interpretation of sub-molecular resolution imaging has been the explicit consideration of deflection (i.e., mechanical deformation) in the tip–sample junction [5][6][7], which can result in contrast enhancement [6

• experimental system to which we compare our results. Typically, in sub-molecular resolution imaging experiments, well defined atoms (such as Xe or Cl), or molecules (such as CO) are picked up from metal surfaces onto metal-coated tips by STM protocols [3]. In our experimental data the initial tip termination

Electrospray deposition of organic molecules on bulk insulator surfaces

• Antoine Hinaut,
• Rémy Pawlak,
• Ernst Meyer and
• Thilo Glatzel

Beilstein J. Nanotechnol. 2015, 6, 1927–1934, doi:10.3762/bjnano.6.195

• techniques are compatible with molecular resolution, the pollution from solvents remains a problem [3][4][5]. Electrospray ionization (ESI), first developed by Fenn et al. [6] allows for the introduction of large organic molecules in vacuum. Originally developed for mass spectrometry and protein studies, it

• surface. Due to the small amount of species on the surface we lowered the charging effect. In this way, we demonstrated the deposition of single molecules, down to few units per 100 × 100 nm2. For some adsorption geometries, where the molecules are laying flat on the surface, we obtained intra-molecular

• resolution at room temperature. Experimental All experiments were performed under UHV conditions (p < 10−10 bar) with our home-built non-contact atomic force microscope (nc-AFM), operating at room temperature (RT) [48]. Bulk insulator KBr(001) crystals surfaces (from MaTeck GmbH) were prepared in situ by

Nanocavity crossbar arrays for parallel electrochemical sensing on a chip

• Enno Kätelhön,
• Dirk Mayer,
• Marko Banzet,
• Andreas Offenhäusser and
• Bernhard Wolfrum

Beilstein J. Nanotechnol. 2014, 5, 1137–1143, doi:10.3762/bjnano.5.124

• limits; Recently, Lemay’s group reported the ultimate detection limit by sensing at molecular resolution inside a nanofluidic redox cycling device [14][15][16]. Besides the advantages of electrochemical amplification, redox cycling sensors allow for the formation of large, dense arrays of electrochemical

Uncertainties in forces extracted from non-contact atomic force microscopy measurements by fitting of long-range background forces

• Adam Sweetman and
• Andrew Stannard

Beilstein J. Nanotechnol. 2014, 5, 386–393, doi:10.3762/bjnano.5.45

• to obtain the desired quantity. In this paper the focus primarily concerns the imaging and quantitative interpretation of atomic or molecular resolution NC-AFM experiments conducted in ultrahigh vacuum (UHV). In these experiments, the quantity of interest is usually the site-specific/short-range

• the molecule is imaged at a low setpoint to reduce the chance of perturbing the tip state, and consequently no sub-molecular resolution is obtained. After obtaining the image, single point Δf(z) spectra were taken on the silicon adatoms, the cornerholes, on top of the molecule, and ‘off’ the molecule

• ‘off’ curve is available, using a conventional silicon cantilever NC-AFM setup. A) Constant Δf NC-AFM image of a C60 molecule adsorbed on the Si(111)-(7 × 7) surface showing atomic and molecular resolution. The position of the white arrow shows where the Δf setpoint was changed from Δf = −53 Hz

Dipole-driven self-organization of zwitterionic molecules on alkali halide surfaces

• Laurent Nony,
• Franck Bocquet,
• Franck Para,
• Frédéric Chérioux,
• Eric Duverger,
• Frank Palmino,
• Vincent Luzet and
• Christian Loppacher

Beilstein J. Nanotechnol. 2012, 3, 285–293, doi:10.3762/bjnano.3.32

• the inset. (a) Topography image of ≈1 ML of MSPS adsorbed on KCl (Δf = −75 Hz, A0 = 7 nm); (b) shows a close up view on an MSPS island boundary with both, the MSPS and the KCl substrate imaged with molecular resolution (Δf = −17 Hz, A0 = 5 nm). (c) Fourier transform of the image displayed in (b), two

Molecular-resolution imaging of pentacene on KCl(001)

• Julia L. Neff,
• Jan Götzen,
• Enhui Li,
• Michael Marz and
• Regina Hoffmann-Vogel

Beilstein J. Nanotechnol. 2012, 3, 186–191, doi:10.3762/bjnano.3.20

• -lying molecules. These order in a commensurable superstructure with respect to the surface pattern. The growth of multilayers depends on the structural details of the substrate. A recent SFM study has shown the morphology of thin pentacene films on Cu(111) with molecular resolution [25]. On graphite

• the undisturbed island. This line defect shows the true molecular resolution of pattern I. For pattern II a point-like defect is displayed in Figure 3a. Here, a darker area is observed with the size of half a unit cell. We attribute this defect to a molecular vacancy caused by one missing molecule

• . This defect shows that also for pattern II true molecular resolution is obtained. The dissipation contrast in Figure 2b shows that the images were obtained at rather close tip–sample distances. At such small distances the positions of the molecules could be influenced reversibly by the interaction with

Direct monitoring of opto-mechanical switching of self-assembled monolayer films containing the azobenzene group

• Einat Tirosh,
• Enrico Benassi,
• Silvio Pipolo,
• Marcel Mayor,
• Michal Valášek,
• Veronica Frydman,
• Stefano Corni and
• Sidney R. Cohen

Beilstein J. Nanotechnol. 2011, 2, 834–844, doi:10.3762/bjnano.2.93

• ↔trans switching have been demonstrated for SAMs. These include mechanical testing, as mentioned above, as well as changes in the local surface potential [13][14], UV–vis spectroscopy [10], wettability [15], and direct molecular-resolution imaging by scanning tunneling microscopy [10]. These methods vary

STM study on the self-assembly of oligothiophene-based organic semiconductors

• Elena Mena-Osteritz,
• Marta Urdanpilleta,
• Erwaa El-Hosseiny,
• Berndt Koslowski,
• Paul Ziemann and
• Peter Bäuerle

Beilstein J. Nanotechnol. 2011, 2, 802–808, doi:10.3762/bjnano.2.88

• -healing process to form a perfectly ordered monolayer over several micrometers. Figure 3 (center) shows a small-scale image of a single domain. The molecular resolution allows the determination of the unit-cell parameters: a = 5.3 ± 0.1 nm, b = 3.0 ± 0.1 nm and α = 29 ± 2°. In the unit cell two molecules

Intermolecular vs molecule–substrate interactions: A combined STM and theoretical study of supramolecular phases on graphene/Ru(0001)

• Michael Roos,
• Benedikt Uhl,
• Daniela Künzel,
• Harry E. Hoster,
• Axel Groß and
• R. Jürgen Behm

Beilstein J. Nanotechnol. 2011, 2, 365–373, doi:10.3762/bjnano.2.42

• '-BTP adlayer on graphene/Ru(0001), with sub-molecular resolution. We can clearly identify the molecules and the hexagonally arranged hills of the graphene adlayer (see marked triangle). The molecules are exclusively adsorbed in the valleys of the graphene film, while the hills remain unoccupied. This

• molecule (Figure 5a–c). These voids indicate that the graphene/Ru(0001) substrate also exhibits a significant corrugation in the adsorption potential for PTCDA, although this is less pronounced, relative to intermolecular interactions, than for 3,3'-BTP. Figure 5c shows a sub-molecular resolution image of

• PTCDA molecules. Fuzzy impression of molecules on hills indicative of (frustrated) rotation (UT = −0.88 V, IT = 50 pA, T = 125 K, 19 nm × 19 nm). (c) Sub-molecular resolution image revealing the adsorption geometry of the PTCDA molecules. (8 nm × 8 nm, UT = 0.97 V, IT = 110 pA, T = 125 K) (d) Model of

Oriented growth of porphyrin-based molecular wires on ionic crystals analysed by nc-AFM

• Thilo Glatzel,
• Lars Zimmerli,
• Shigeki Kawai,
• Ernst Meyer,
• Leslie-Anne Fendt and
• Francois Diederich

Beilstein J. Nanotechnol. 2011, 2, 34–39, doi:10.3762/bjnano.2.4

• layers. (b) and (c) 30 × 30 nm2 zoom in of the free standing molecular assembly on a single KBr layer. Clear sub-molecular resolution as well as atomic resolution is observed. After decreasing the set-point, parts of the assembly are removed and the atomic corrugation below becomes visible. Chemical

Tip-sample interactions on graphite studied using the wavelet transform

• Giovanna Malegori and
• Gabriele Ferrini

Beilstein J. Nanotechnol. 2010, 1, 172–181, doi:10.3762/bjnano.1.21

• of the cantilever may show a modification of the oscillation amplitude, frequency, phase or damping. The measurement of these cantilever parameters allows to gain information on the physical properties of the sample with (sub-)molecular resolution [4][5]. The dynamic behavior of a weakly interacting