I09-Surface and Interface Structural Analysis
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Aleksandr
Baklanov
,
Johannes T.
Kuchle
,
David A.
Duncan
,
Reinhard J.
Maurer
,
Martin
Schwarz
,
Eduardo Corral
Rascon
,
Ignacio
Piquero-Zulaica
,
Huynh Thien
Ngo
,
Alexander
Riss
,
Francesco
Allegretti
,
Willi
Auwärter
,
Paul T. P.
Ryan
Diamond Proposal Number(s):
[18874, 24276]
Abstract: We present a comprehensive, quantitative multimethod characterization of the geometric and electronic interfacial structure of zinc-porphine (Zn-P) on coinage metal supports, namely, Ag(111) and Cu(111). Complementary techniques including X-ray standing waves, X-ray photoelectron spectroscopy, scanning tunneling microscopy, bond-resolved atomic force microscopy, and density functional theory calculations reveal the molecular conformations, signal a temperature-dependence of element-specific adsorption heights, rule out a decisive role of the d10 nature of the Zn center for the adsorption configuration, and uncover a considerably increased Zn-P adsorption height on Ag(111) compared to Cu(111). Furthermore, a pronounced out-of-plane displacement of the Zn center upon water ligation is demonstrated, a manifestation of the surface trans-effect. This study thus sheds light on effects of temperature, chemical nature of the metal center, its ligation, and the coinage metal support on interfacial structure and molecular deformation of an archetypical surface-anchored metal-tetrapyrrole.
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Apr 2023
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I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[17261, 20785]
Open Access
Abstract: The results are presented of a detailed combined experimental and theoretical investigation of the influence of coadsorbed electron-donating alkali atoms and the prototypical electron acceptor molecule 7,7,8,8-tetracyanoquinodimethane (TCNQ) on the Ag(100) surface. Several coadsorption phases were characterized by scanning tunneling microscopy, low-energy electron diffraction, and soft X-ray photoelectron spectroscopy. Quantitative structural data were obtained using normal-incidence X-ray standing wave (NIXSW) measurements and compared with the results of density functional theory (DFT) calculations using several different methods of dispersion correction. Generally, good agreement between theory and experiment was achieved for the quantitative structures, albeit with the prediction of the alkali atom heights being challenging for some methods. The adsorption structures depend sensitively on the interplay of molecule–metal charge transfer and long-range dispersion forces, which are controlled by the composition ratio between alkali atoms and TCNQ. The large difference in atomic size between K and Cs has negligible effects on stability, whereas increasing the ratio of K/TCNQ from 1:4 to 1:1 leads to a weakening of molecule–metal interaction strength in favor of stronger ionic bonds within the two-dimensional alkali–organic network. A strong dependence of the work function on the alkali donor–TCNQ acceptor coadsorption ratio is predicted.
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Jan 2023
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I09-Surface and Interface Structural Analysis
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Diamond Proposal Number(s):
[18398]
Abstract: Using the normal incidence x-ray standing-wave technique as well as low-energy electron microscopy we have investigated the structure of quasifreestanding monolayer graphene (QFMLG) obtained by intercalation of antimony under the
(
6
√
3
×
6
√
3
)
R
30
∘
reconstructed graphitized
6
H
-SiC(0001) surface, also known as zeroth-layer graphene. We found that Sb intercalation decouples the QFMLG well from the substrate. The distance from the QFMLG to the Sb layer almost equals the expected van der Waals bonding distance of C and Sb. The Sb intercalation layer itself is monoatomic, flat, and located much closer to the substrate, at almost the distance of a covalent Sb-Si bond length. All data is consistent with Sb located on top of the uppermost Si atoms of the SiC bulk.
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Oct 2022
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I09-Surface and Interface Structural Analysis
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Peter
Knecht
,
Dennis
Meier
,
Joachim
Reichert
,
David A.
Duncan
,
Martin
Schwarz
,
Johannes
Kuchle
,
Tien-Lin
Lee
,
Peter
Deimel
,
Peter
Feulner
,
Francesco
Allegretti
,
Willi
Auwärter
,
Guillaume
Médard
,
Ari P.
Seitsonen
,
Johannes V.
Barth
,
Anthoula
Papageorgiou
Diamond Proposal Number(s):
[17634]
Open Access
Abstract: Ru-porphyrins act as convenient pedestals for the assembly of N-heterocyclic carbenes (NHCs) on solid surfaces. Upon deposition of a simple NHC ligand on a close packed Ru-porphyrin monolayer, an extraordinary phenomenon can be observed: Ru-porphyrin molecules are transferred from the silver surface to the next molecular layer. We have investigated the structural features and dynamics of this portering process and analyzed the associated binding strengths and work function changes. A rearrangement of the molecular layer is induced by the NHC uptake: the NHC selective binding to the Ru atoms causes the ejection of whole porphyrin molecules from the molecular layer on silver to the layer on top. This reorganization can be reversed by thermally induced desorption of the NHC ligand. We anticipate that the understanding of such mass transport processes will have crucial implications for the functionalization of surfaces with carbenes.
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Oct 2022
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I09-Surface and Interface Structural Analysis
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Abstract: Although scanning probe microscopy (SPM) techniques have allowed researchers to interact with the nanoscale for decades now, little improvement has been made to the incredibly manual, time consuming process of setting up, running, and analysing the results of these experiments, often arising due to the constantly varying shape of the probe apex. Unlike traditional computing methods, machine learning methods (with neural networks in particular) are considerably more capable of automating subjective tasks such as these, and we are only just beginning to explore the potential applications of this technology in SPM. In this thesis we explore a number of areas where machine learning could potentially massively change the way we go about SPM experimentation. We begin by discussing the history, theory, and experimental concepts of scanning tunnelling microscopy (STM), atomic force microscopy (AFM), and normal-incidence-x-ray standing wave (NIXSW). We then explore the makeup of a neural network and demonstrate how they can be applied to a variety of use-cases in SPM, including classification and policy prediction. Moving to the experimental chapters, we first discuss how we can successfully distinguish between STM tip states of the H:Si(100), Au(111) and Cu(111) surfaces. We also show that by adapting this network to work in real time, we improve performance while requiring on the order of 100x less data. We next discuss our attempts to combine these networks with expert examples to intelligently maintain tip apex sharpness during experimentation, envisioning an end-to-end automatic experiment. Because one of the main difficulties in applying machine learning is the frequent need to manually label data, we then show how we can use Monte Carlo simulations of self-organised AFM nanostructures to automatically label training data for a network, and then combine it with classical statistics and preprocessing to find specific structures in a mixed, messy dataset of real, experimental AFM images. As part of this, we also build a network to denoise experimental images. Finally, we present NIXSW results from an investigation into the temperature dependence of H20@C60, discussing the potential to use unsupervised clustering techniques to distinguish between noisy human-indistinguishable spectra to overcome limitations in data collection.
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Aug 2022
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I09-Surface and Interface Structural Analysis
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Johannes T.
Küchle
,
Aleksandr
Baklanov
,
Ari Paavo
Seitsonen
,
Paul
Ryan
,
Peter
Feulner
,
Prashanth
Pendem
,
Tien-Lin
Lee
,
Matthias
Muntwiler
,
Martin
Schwarz
,
Felix
Haag
,
Johannes V
Barth
,
Willi
Auwärter
,
David A.
Duncan
,
Francesco
Allegretti
Diamond Proposal Number(s):
[15804, 20771]
Open Access
Abstract: Silicene, the two-dimensional (2D) allotrope of silicon, is a promising material for electronics. So far, the most direct synthesis strategy has been to grow it epitaxially on metal surfaces; however, the effect of the strong silicon-metal interaction on the structure and electronic properties of the metal-supported silicene is generally poorly understood. In this work, we consider the 4×4-silicene monolayer grown on Ag(111), probably the most illustrious representative of the 2D silicon family, and show that our experimental results refute the common interpretation of this system as a simple buckled, honeycomb monolayer with a sharp interface to the Ag substrate. Instead, the presented analysis demonstrates the pervasive presence of a second silicon species, which we conclude to be a Si‑Ag alloy stacked between the 2D silicene and the silver substrate and scaffolding the 2D silicene layer. These findings question the current structural understanding of the silicene/Ag(111) interface and may raise expectations of analogous alloy systems in the stabilization of other 2D materials grown epitaxially on metal surfaces.
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Aug 2022
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I09-Surface and Interface Structural Analysis
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You-Ron
Lin
,
Markus
Franke
,
Shayan
Parhizkar
,
Miriam
Raths
,
Victor
Wen-Zhe Yu
,
Tien-Lin
Lee
,
Serguei
Soubatch
,
Volker
Blum
,
F. Stefan
Tautz
,
Christian
Kumpf
,
Francois C.
Bocquet
Diamond Proposal Number(s):
[17737]
Abstract: In the field of van der Waals heterostructures, the twist angle between stacked two-dimensional layers has been identified to be of utmost importance for the properties of the heterostructures. In this context, we previously reported the growth of a single layer of unconventionally oriented epitaxial graphene that forms in a surfactant atmosphere [F. C. Bocquet et al., Phys. Rev. Lett. 125, 106102 (2020)]. The resulting G-
R
0
∘
layer is aligned with the SiC lattice, and hence represents an important milestone towards high-quality twisted bilayer graphene, a frequently investigated model system in this field. Here, we focus on the surface structures obtained in the same surfactant atmosphere, but at lower preparation temperatures at which a boron nitride template layer forms on SiC(0001). In a comprehensive study based on complementary experimental and theoretical techniques, we find—in contrast to the literature—that this template layer is a hexagonal
B
x
N
y
layer, but not high-quality hBN. It is aligned with the SiC lattice and gradually replaced by low-quality graphene in the
0
∘
orientation of the
B
x
N
y
template layer upon annealing.
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Jun 2022
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I09-Surface and Interface Structural Analysis
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Diamond Proposal Number(s):
[16243]
Open Access
Abstract: A combined high resolution X-ray photoelectron spectroscopy and X-ray standing wave study into the adsorption structure of hydrogenated graphene on Ir(111) is presented. By exploiting the unique absorption profiles and significant modulations in signal intensity found within the X-ray standing wave results, we refine the fitting of the C 1s X-ray photoelectron spectra, allowing us to disentangle the contributions from hydrogenation of graphene in different high-symmetry regions of the moiré supercell. We clearly demonstrate that hydrogenation in the FCC regions results in the formation of a graphane-like structure, giving a standalone component that is separated from the component assigned to the similar structure in the HCP regions. The contribution from dimer structures in the ATOP regions is found to be minor or negligible. This is in contrast to the previous findings where a dimer structure was assumed to contribute significantly to the sp3 part of the C 1s spectra. The corrugation of the remaining pristine parts of the H-graphene is shown to increase with the H coverage, reflecting an increasing number and size of pinning centers of the graphene to the Ir(111) substrate with increasing H exposure.
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May 2022
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I09-Surface and Interface Structural Analysis
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Diamond Proposal Number(s):
[20076]
Abstract: X-ray standing-wave (XSW) excited photoelectron emission was used to measure the site-specific valence band (VB) for ½ monolayer (ML) Pt grown on a
SrTiO
3
(001) surface. The XSW induced modulations in the core level (CL), and VB photoemission from the surface and substrate atoms were monitored for three
h
k
l
substrate Bragg reflections. The XSW CL analysis shows the Pt to have a face-centered-cubic-like cube-on-cube epitaxy with the substrate. The XSW VB information compares well to a density functional theory calculated projected density of states from the surface and substrate atoms. Overall, this Letter represents a novel method for determining the contribution to the density of states by valence electrons from specific atomic surface sites.
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May 2022
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I07-Surface & interface diffraction
I09-Surface and Interface Structural Analysis
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Philip J.
Mousley
,
Luke A.
Rochford
,
Paul T. P.
Ryan
,
Philip
Blowey
,
James
Lawrence
,
David A.
Duncan
,
Hadeel
Hussain
,
Billal
Sohail
,
Tien-Lin
Lee
,
Gavin R.
Bell
,
Giovanni
Costantini
,
Reinhard J.
Maurer
,
Christopher
Nicklin
,
D. Phil
Woodruff
Diamond Proposal Number(s):
[14884, 4884]
Open Access
Abstract: While the phenomenon of metal substrate adatom incorporation into molecular overlayers is generally believed to occur in several systems, the experimental evidence for this relies on the interpretation of scanning tunneling microscopy (STM) images, which can be ambiguous and provides no quantitative structural information. We show that surface X-ray diffraction (SXRD) uniquely provides unambiguous identification of these metal adatoms. We present the results of a detailed structural study of the Au(111)-F4TCNQ system, combining surface characterization by STM, low-energy electron diffraction, and soft X-ray photoelectron spectroscopy with quantitative experimental structural information from normal incidence X-ray standing wave (NIXSW) and SXRD, together with dispersion-corrected density functional theory (DFT) calculations. Excellent agreement is found between the NIXSW data and the DFT calculations regarding the height and conformation of the adsorbed molecule, which has a twisted geometry rather than the previously supposed inverted bowl shape. SXRD measurements provide unequivocal evidence for the presence and location of Au adatoms, while the DFT calculations show this reconstruction to be strongly energetically favored.
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Apr 2022
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