I09-Surface and Interface Structural Analysis
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Diamond Proposal Number(s):
[15899, 18191]
Abstract: The structure of coadsorption phases formed on Ag(111) by TCNQ (7,7,8,8-tetracyanoquinodimethane) with Cs are compared with previously reported coadsorption phases formed with K, following investigation by scanning tunnelling microscopy (STM), low energy electron diffraction, soft X-ray photoelectrons spectroscopy and normal incidence X-ray standing waves (NIXSW). For each alkali we identify two ordered phases, one with an alkali: TCNQ stoichiometry of 1:1 and the other 2:1. STM images show the molecular organisation is the same for Cs and K, although only the K2TCNQ phase is commensurate with the substrate. A previously-published detailed structure determination of the K2TCNQ phase, complemented by density function theory calculations that identify bonding strengths, showed that the binding within the layer is much stronger than that of the layer to the substrate. Insensitivity to commensuration is thus to be expected. The situation for KTCNQ and CsTCNQ is less clear; these ordered incommensurate overlayers clearly have strong intralayer bonding, but the relative strength of the average overlayer-substrate bonding is unknown. NIXSW data show that the alkalis in these phases occupy adsorption sites far more distant from the substrate than the TCNQ molecules when compared to the near coplanar alkali-TCNQ geometry of K2TCNQ and Cs2TCNQ. Ultraviolet photoelectron spectra show increasing bonding shifts of TCNQ orbital states with alkali coverage.
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Nov 2020
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I09-Surface and Interface Structural Analysis
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Jack E. N.
Swallow
,
Christian
Vorwerk
,
Piero
Mazzolini
,
Patrick
Vogt
,
Oliver
Bierwagen
,
Alexander
Karg
,
Martin
Eickhoff
,
Jörg
Schörmann
,
Markus R.
Wagner
,
Joseph William
Roberts
,
Paul R.
Chalker
,
Matthew J.
Smiles
,
Philip
Murgatroyd
,
Sara
Mohamed
,
Zachary W.
Lebens-higgins
,
Louis F. J.
Piper
,
Leanne A. H.
Jones
,
Pardeep K.
Thakur
,
Tien-lin
Lee
,
Joel B.
Varley
,
Juergen
Furthmüller
,
Claudia
Draxl
,
Tim D.
Veal
,
Anna
Regoutz
Diamond Proposal Number(s):
[21430, 24670]
Abstract: The search for new wide band gap materials is intensifying to satisfy the need for more advanced and energy effcient power electronic devices. Ga2O3 has emerged as an alternative to SiC and GaN, sparking a renewed interest in its fundamental properties beyond the main β-phase. Here, three polymorphs of Ga2O3, α, β, and ε, are investigated using X-ray diffraction, X-ray photoelectron and absorption spectroscopy, and ab initio theoretical approaches to gain insights into their structure - electronic structure relationships. Valence and conduction electronic structure as well as semi-core and core states are probed, providing a complete picture of the influence of local coordination environments on the electronic structure. State-of-the-art electronic structure theory, including all-electron density functional theory and many-body perturbation theory, provide detailed understanding of the spectroscopic results. The calculated spectra provide very accurate descriptions of all experimental spectra and additionally illuminate the origin of observed spectral features. This work provides a strong basis for the exploration of the Ga2O3 polymorphs as materials at the heart of future electronic device generations.
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Sep 2020
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I09-Surface and Interface Structural Analysis
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Diamond Proposal Number(s):
[16243]
Open Access
Abstract: Interesting electronic properties arise in vertically stacked graphene sheets, some of which can be controlled by mutual orientation of the adjacent layers. In this study, we investigate the MBE grown multilayer graphene on Ir(111) by means of STM, LEED and XPS and we examine the influence of the substrate on the geometric and electronic properties of bilayer graphene by employing XSW and ARPES measurements. We find that the MBE method does not limit the growth to two graphene layers and that the wrinkles, which arise through extended carbon deposition, play a crucial role in the multilayer growth. We also find that the bilayer and trilayer graphene sheets have graphitic-like properties in terms of the separation between the two layers and their stacking. The presence of the iridium substrate imposes a periodic potential induced by the moiré pattern that was found to lead to the formation of replica bands and minigaps in bilayer graphene. From tight-binding fits to our ARPES data we find that band renormalization takes place in multilayer graphene due to a weaker coupling of the upper-most graphene layer to the iridium substrate.
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Sep 2020
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I09-Surface and Interface Structural Analysis
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Diamond Proposal Number(s):
[17737, 20810, 20855]
Abstract: We report the use of a surfactant molecule during the epitaxy of graphene on SiC(0001) that leads to the growth in an unconventional orientation, namely
R
0
°
rotation with respect to the SiC lattice. It yields a very high-quality single-layer graphene with a uniform orientation with respect to the substrate, on the wafer scale. We find an increased quality and homogeneity compared to the approach based on the use of a preoriented template to induce the unconventional orientation. Using spot profile analysis low-energy electron diffraction, angle-resolved photoelectron spectroscopy, and the normal incidence x-ray standing wave technique, we assess the crystalline quality and coverage of the graphene layer. Combined with the presence of a covalently bound graphene layer in the conventional orientation underneath, our surfactant-mediated growth offers an ideal platform to prepare epitaxial twisted bilayer graphene via intercalation.
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Sep 2020
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I09-Surface and Interface Structural Analysis
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Christopher H.
Don
,
Huw
Shiel
,
Theodore D. C.
Hobson
,
Christopher N.
Savory
,
Jack E. N.
Swallow
,
Matthew J.
Smiles
,
Leanne A. H.
Jones
,
Thomas J.
Featherstone
,
Pardeep K.
Thakur
,
Tien-lin
Lee
,
Ken
Durose
,
Jonathan D.
Major
,
Vinod R.
Dhanak
,
David O.
Scanlon
,
Tim D.
Veal
Diamond Proposal Number(s):
[21431]
Open Access
Abstract: The presence of a lone pair of 5s electrons at the valence band maximum (VBM) of Sb2Se3 and the resulting band alignments are investigated using soft and hard X-ray photoemission spectroscopy in parallel with density functional theory (DFT) calculations. Vacuum-cleaved and exfoliated bulk crystals of Sb2Se3 are analysed using laboratory and synchrotron X-ray sources to acquire high resolution valence band spectra with both soft and hard X-rays. Utilising the photon-energy dependence of different orbital cross-sections and corresponding DFT calculations, the various orbital contributions to the valence band could be identified, including the 5s orbital's presence at the VBM. The ionization potential is also determined and places the VBM at 5.13 eV below the vacuum level, similar to other materials with 5s2 lone pairs, but far above those of related materials without lone pairs of electrons.
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Aug 2020
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I09-Surface and Interface Structural Analysis
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Leanne A. H.
Jones
,
Wojciech M.
Linhart
,
Nicole
Fleck
,
Jack E. N.
Swallow
,
Philip A. E.
Murgatroyd
,
Huw
Shiel
,
Thomas J.
Featherstone
,
Matthew J.
Smiles
,
Pardeep K.
Thakur
,
Tien-lin
Lee
,
Laurence J.
Hardwick
,
Jonathan
Alaria
,
Frank
Jaeckel
,
Robert
Kudrawiec
,
Lee A.
Burton
,
Aron
Walsh
,
Jonathan M.
Skelton
,
Tim D.
Veal
,
Vin R.
Dhanak
Diamond Proposal Number(s):
[21431]
Open Access
Abstract: The effects of Sn
5
s
lone pairs in the different phases of Sn sulphides are investigated with photoreflectance, hard x-ray photoemission spectroscopy (HAXPES), and density functional theory. Due to the photon energy-dependence of the photoionization cross sections, at high photon energy, the Sn
5
s
orbital photoemission has increased intensity relative to that from other orbitals. This enables the Sn
5
s
state contribution at the top of the valence band in the different Sn-sulphides, SnS,
Sn
2
S
3
, and
SnS
2
, to be clearly identified. SnS and
Sn
2
S
3
contain Sn(II) cations and the corresponding Sn
5
s
lone pairs are at the valence band maximum (VBM), leading to
∼
1.0
–1.3 eV band gaps and relatively high VBM on an absolute energy scale. In contrast,
SnS
2
only contains Sn(IV) cations, no filled lone pairs, and therefore has a
∼
2.3
eV room-temperature band gap and much lower VBM compared with SnS and
Sn
2
S
3
. The direct band gaps of these materials at 20 K are found using photoreflectance to be 1.36, 1.08, and 2.47 eV for SnS,
Sn
2
S
3
, and
SnS
2
, respectively, which further highlights the effect of having the lone-pair states at the VBM. As well as elucidating the role of the Sn
5
s
lone pairs in determining the band gaps and band alignments of the family of Sn-sulphide compounds, this also highlights how HAXPES is an ideal method for probing the lone-pair contribution to the density of states of the emerging class of materials with
n
s
2
configuration.
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Jul 2020
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I09-Surface and Interface Structural Analysis
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Minh Hai
Tran
,
Ali M.
Malik
,
Michael
Dürrschnabel
,
Anna
Regoutz
,
Pardeep
Thakur
,
Tien-lin
Lee
,
Delwin
Perera
,
Leopoldo
Molina-luna
,
Karsten
Albe
,
Jochen
Rohrer
,
Christina S.
Birkel
Diamond Proposal Number(s):
[24670]
Abstract: Two-dimensional carbides/nitrides, typically called MXenes, are an emerging member of the ever-growing family of two-dimensional materials. The prediction of a ferromagnetic groundstate in chromium-containing MXenes has triggered growing interest in their chemical exfoliation from Cr-based MAX phases. However, the exfoliation poses serious difficulties using standard etching agents such as hydrofluoric acid (HF). Here, we investigate the exfoliability of Cr2GaC particles by chemical etching with aqueous HF both experimentally and theoretically. Structural and microstructural analyses show that the Cr2GaC particles decompose into chromium carbide and oxide without the formation of a Cr-based MXene. A thermodynamic analysis based on ab initio electronic structure calculations reveals that the exfoliation of Cr-based MXene from Cr2GaC by HF-etching is inhibited by more favorable competing reactions. This result confirms the experimental finding and suggests that HF is an unsuitable etching agent for a successful exfoliation of Cr2GaC.
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Jul 2020
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I09-Surface and Interface Structural Analysis
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Celso I.
Fornari
,
Hendrik
Bentmann
,
Sergio L.
Morelhao
,
Thiago R. F.
Peixoto
,
Paulo
Rappl
,
Abdul
Tcakaev
,
Volodymyr
Zabolotnyy
,
Martin
Kamp
,
Tien-lin
Lee
,
Chul-hee
Min
,
Philipp
Kagerer
,
Raphael
Vidal
,
Anna
Isaeva
,
Michael
Ruck
,
Vladimir
Hinkov
,
Friedrich
Reinert
,
Eduardo
Abramof
Abstract: In the field of topological materials, the interaction between band topology and magnetism remains a current frontier for the advance of new topological states and spintronic functionalities. Doping with rare-earth elements with large magnetic moment is a current approach to exploit the phenomenology of such interaction. However, dopant solubility into the main matrix plays a major role. In this sense, the present work is focused on elucidating how Eu incorporates into Bi2Te3 lattice as a function of doping. This work reports a systematic investigation of the structural and electronic properties of bismuth telluride epitaxial layers doped with Eu. Bi2Te3 films were grown by molecular beam epitaxy (MBE) on (111) BaF2 substrates with nominal Eu doping ranging from 0 % up to 9 %. X-ray diffraction (XRD) analysis and scanning transmission electron microscopy (TEM) reveal that Eu atoms enter substitutionally on Bi sites up to 4 % of Eu doping. In contrast, the 9 % Eu-doped sample contains epitaxially oriented nanoclusters of EuTe. X ray photoelectron (XPS) and absorption (XAS) spectroscopies show that Eu atoms enter into the Bi2Te3 crystal matrix in the divalent Eu2+ state for all Eu concentrations. Angle resolved photoemission (ARPES) experiments indicate that the topological surface state is preserved in the presence of the local magnetic moments introduced by the Eu impurities.
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Jun 2020
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I09-Surface and Interface Structural Analysis
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Galo J.
Paez
,
Christopher N.
Singh
,
Matthew J.
Wahila
,
Keith E.
Tirpak
,
Nicholas F.
Quackenbush
,
Shawn
Sallis
,
Hanjong
Paik
,
Yufeng
Liang
,
Darrell G.
Schlom
,
Tien-lin
Lee
,
Christoph
Schlueter
,
Wei-cheng
Lee
,
Louis F. J.
Piper
Diamond Proposal Number(s):
[13812, 25355]
Abstract: Recent reports have identified new metaphases of
VO
2
with strain and/or doping, suggesting the structural phase transition and the metal-to-insulator transition might be decoupled. Using epitaxially strained
VO
2
/
Ti
O
2
(001) thin films, which display a bulklike abrupt metal-to-insulator transition and rutile to monoclinic transition structural phase transition, we employ x-ray standing waves combined with hard x-ray photoelectron spectroscopy to simultaneously measure the structural and electronic transitions. This x-ray standing waves study elegantly demonstrates the structural and electronic transitions occur concurrently within experimental limits (±1K).
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May 2020
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I09-Surface and Interface Structural Analysis
|
Phil J.
Blowey
,
Billal
Sohail
,
Luke A.
Rochford
,
Timothy
Lafosse
,
David A.
Duncan
,
Paul
Ryan
,
Daniel Andrew
Warr
,
Tien-lin
Lee
,
Giovanni
Costantini
,
Reinhard J.
Maurer
,
David Phillip
Woodruff
Diamond Proposal Number(s):
[15899, 18191]
Abstract: Efficient charge transfer across metal–organic interfaces is a key physical process in modern organic electronics devices, and characterization of the energy level alignment at the interface is crucial to enable a rational device design. We show that the insertion of alkali atoms can significantly change the structure and electronic properties of a metal–organic interface. Coadsorption of tetracyanoquinodimethane (TCNQ) and potassium on a Ag(111) surface leads to the formation of a two-dimensional charge transfer salt, with properties quite different from those of the two-dimensional Ag adatom TCNQ metal–organic framework formed in the absence of K doping. We establish a highly accurate structural model by combination of quantitative X-ray standing wave measurements, scanning tunnelling microscopy, and density-functional theory (DFT) calculations. Full agreement between the experimental data and the computational prediction of the structure is only achieved by inclusion of a charge-transfer-scaled dispersion correction in the DFT, which correctly accounts for the effects of strong charge transfer on the atomic polarizability of potassium. The commensurate surface layer formed by TCNQ and K is dominated by strong charge transfer and ionic bonding and is accompanied by a structural and electronic decoupling from the underlying metal substrate. The consequence is a significant change in energy level alignment and work function compared to TCNQ on Ag(111). Possible implications of charge-transfer salt formation at metal–organic interfaces for organic thin-film devices are discussed.
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May 2020
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