I09-Surface and Interface Structural Analysis
|
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.
|
Jul 2020
|
|
I09-Surface and Interface Structural Analysis
|
Diamond Proposal Number(s):
[22648]
Open Access
Abstract: We report on the electronic structure of doped LaFeO3 at the crossover from an insulating-to-metallic phase Transition. Comprehensive x-ray spectroscopic methodologies are used to understand core and valence electronic structure as well as crystal structure distortions associated with the electronic transition. Despite the antiferromagnetic (AFM) ordering at room temperature, we show direct evidence of itinerant carriers at the Fermi level revealed by resonant photoemission spectroscopy (RPES) at the Mo L3 edge. RPES data taken at the Fe L3 edge show spectral weight near the valence band edge and significant hybridization with O 2p states required for AFM ordering. Resonant inelastic x-ray scattering spectra taken across Fe L2, 3 edges show electron correlation effects (U) driven by Coulomb interactions of d electrons as well as broad charge-transfer excitations for x > 0.2 where the compound crosses over to a metallic state. Site substitution of Fe by Mo ions in the Fe-O6 octahedra enhances the separation of the two Fe-O bonds and Fe-O-Fe bonding angles relative to the orthorhombic
LaFeO3, but no considerable Distortions are present to the overall structure. Mo ions appear to be homogeneously doped, with average valency of both metal sites monotonically decreasing with increasing Mo concentration. This insulator-to-metal phase transition with AFM stability is primarily understood through intermediate interaction strengths between correlation (U) and bandwidth (W) at the Fe site, where an estimation of this ratio is given. These results highlight the important role of extrinsic carriers in stabilizing a unique phase transition that can guide future efforts in antiferromagnetic-metal spintronics.
|
Mar 2020
|
|
I09-Surface and Interface Structural Analysis
I10-Beamline for Advanced Dichroism
|
Georgios
Araizi-kanoutas
,
Jaap
Geessinck
,
Nicolas
Gauquelin
,
Steef
Smit
,
Xanthe H.
Verbeek
,
Shrawan K.
Mishra
,
Peter
Bencok
,
Christoph
Schlueter
,
Tien-lin
Lee
,
Dileep
Krishnan
,
Jarmo
Fatermans
,
Jo
Verbeeck
,
Guus
Rijnders
,
Gertjan
Koster
,
Mark S.
Golden
Abstract: We report charge transfer up to a single electron per interfacial unit cell across nonpolar heterointerfaces from the Mott insulator
LaTi
O
3
to the charge transfer insulator
LaCo
O
3
. In high-quality bi- and trilayer systems grown using pulsed laser deposition, soft x-ray absorption, dichroism, and scanning transmission electron microscopy-electron energy loss spectroscopy are used to probe the cobalt-
3
d
electron count and provide an element-specific investigation of the magnetic properties. The experiments show the cobalt valence conversion is active within 3 unit cells of the heterointerface, and able to generate full conversion to
3
d
7
divalent Co, which displays a paramagnetic ground state. The number of
LaTi
O
3
/
LaCo
O
3
interfaces, the thickness of an additional, electronically insulating “break” layer between the
LaTi
O
3
and
LaCo
O
3
, and the
LaCo
O
3
film thickness itself in trilayers provide a trio of control knobs for average charge of the cobalt ions in
LaCo
O
3
, illustrating the efficacy of
O
−
2
p
band alignment as a guiding principle for property design in complex oxide heterointerfaces.
|
Feb 2020
|
|
I09-Surface and Interface Structural Analysis
|
Jens
Niederhausen
,
Antoni
Franco-cañellas
,
Simon
Erker
,
Thorsten
Schultz
,
Katharina
Broch
,
Alexander
Hinderhofer
,
Steffen
Duhm
,
Pardeep K.
Thakur
,
David A.
Duncan
,
Alexander
Gerlach
,
Tien-lin
Lee
,
Oliver T.
Hofmann
,
Frank
Schreiber
,
Norbert
Koch
Diamond Proposal Number(s):
[11415, 13740, 19033]
Open Access
Abstract: The vertical adsorption distances of the planar conjugated organic molecule 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) on hydroxylated ZnO(0001), determined with the x-ray standing wave technique (XSW), are at variance with adsorption geometries simulated with density functional theory for surface-structure models that consider terminating OH, whereas good agreement is found for PTCDI in direct contact with the topmost Zn layer. The consequential assignment of OH to subsurface sites is supported by additional, independent XSW and energy scanned photoelectron diffraction data and calls for a reconsideration of the prevalent surface models with important implications for the understanding of ZnO(0001) surfaces.
|
Feb 2020
|
|
I06-Nanoscience
|
Diamond Proposal Number(s):
[17588]
Abstract: Magnetite (
Fe
3
O
4
) thin-films are among the most stimulating systems for electronic applications, in particular given that their electric and magnetic properties can be controlled by substrate strain. Here we investigate the electronic structure of a 38 nm
Fe
3
O
4
/
SrTiO
3
(
001
)
thin-film by a unique set of x-ray magnetic linear dichroism (XMLD) measurements. We show that it is only possible to uncover the orbital character of the Fe sites in
Fe
3
O
4
by a systematic analysis of the XMLD angular distribution. The local symmetry of the
Fe
2
+
B site in the thin-film is found to be trigonally distorted. Our results highlight that the combination of state-of-the-art XMLD measurements and theoretical simulations is indispensable for investigating the electronic structure of oxide thin-films and heterostructures.
|
Feb 2020
|
|
I09-Surface and Interface Structural Analysis
|
Chiara
Bigi
,
Zhenkun
Tang
,
Gian Marco
Pierantozzi
,
Pasquale
Orgiani
,
Pranab Kumar
Das
,
Jun
Fujii
,
Ivana
Vobornik
,
Tommaso
Pincelli
,
Alessandro
Troglia
,
Tien-lin
Lee
,
Regina
Ciancio
,
Goran
Drazic
,
Alberto
Verdini
,
Anna
Regoutz
,
Phil D. C.
King
,
Deepnarayan
Biswas
,
Giorgio
Rossi
,
Giancarlo
Panaccione
,
Annabella
Selloni
Diamond Proposal Number(s):
[16041]
Abstract: Two-dimensional (2D) metallic states induced by oxygen vacancies (
V
O
s
) at oxide surfaces and interfaces provide opportunities for the development of advanced applications, but the ability to control the behavior of these states is still limited. We used angle resolved photoelectron spectroscopy combined with density-functional theory (DFT) to study the reactivity of
V
O
-induced states at the (001) surface of anatase
TiO
2
, where both 2D metallic and deeper lying in-gap states (IGs) are observed. The 2D and IG states exhibit remarkably different evolutions when the surface is exposed to molecular
O
2
: while IGs are almost completely quenched, the metallic states are only weakly affected. DFT calculations indeed show that the IGs originate from surface
V
O
s
and remain localized at the surface, where they can promptly react with
O
2
. In contrast, the metallic states originate from subsurface vacancies whose migration to the surface for recombination with
O
2
is kinetically hindered on anatase
TiO
2
(001), thus making them much less sensitive to oxygen dosing.
|
Feb 2020
|
|
I09-Surface and Interface Structural Analysis
|
David A.
Duncan
,
Nicolae
Atodiresei
,
Simone
Lisi
,
Phil J.
Blowey
,
Vasile
Caciuc
,
James
Lawrence
,
Tien-lin
Lee
,
Maria Grazia
Betti
,
Pardeep Kumar
Thakur
,
Ada
Della Pia
,
Stefan
Blügel
,
Giovanni
Costantini
,
D. Phil
Woodruff
Diamond Proposal Number(s):
[13625]
Open Access
Abstract: Theoretical formulations capable of modeling chemical interactions over 3–4 orders of magnitude of bond strength, from covalent to van der Waals (vdW) forces, are one of the primary goals in materials physics, and chemistry. Development of vdW corrections for density-functional theory has thus been a major research field for two decades. While many of these corrections are semiempirical, more theoretically rigorous ab initio functionals have been developed. The ab initio functional vdW-DF2, when coupled with the reoptimized B86 exchange function (vdW-DF2-rB86), has typically performed as well, if not better than most semiempirical formulations. Here we present a system, Co intercalation of graphene on Ir(111), for which a semiempirical correction predicts local corrugation maxima in locations at which the vdW-DF2-rB86 functional predicts global minima. Sub-angstrom precision quantitative structural measurements show better agreement with the semiempirical correction. We posit that it is balancing the weak vdW interaction with the stronger, even covalent, interactions that proves a challenge for the vdW-DF2-rB86 functional.
|
Dec 2019
|
|
I09-Surface and Interface Structural Analysis
|
Diamond Proposal Number(s):
[12975]
Abstract: A combination of scanning tunneling microscopy, low-energy electron diffraction,and low-energy electron microscopy (LEEM) has been used to identify the structural phases formed by 7,7,8,8-tetracyanoquinodimethane (TCNQ) on Ag(111). These comprise a two-dimensional gas phase, a low-density commensurate (LDC) phase, and a higher-density incommensurate (HDI) phase. LEEM also shows the presence of an additional “precursor-HDI” phase with a surface unit mesh area only ≈3% less than the HDI phase. Normal incidence x-ray standing-wave measurements of the HDI phase yield almost identical structural parameters to the LDC phase for which a full structure determination has been previously reported. The results show TCNQ does not adopt the inverted bowl distortion favored in earlier density functional theory calculations of TCNQ on coinage metal surfaces, but the N atoms are twisted out of the molecular plane, an effect found for the LDC phase to be due to incorporation of Ag adatoms. The possible role of Ag adatoms in the HDI phase, and in the transition from the precursor-HDI phase, is discussed.
|
Nov 2019
|
|
I09-Surface and Interface Structural Analysis
|
Abstract: The electronic properties of
CaCuO
2
/
La
0.7
Sr
0.3
MnO
3
(LSMO) superlattices are determined by the electronic structure of the structural units and in particular their interfaces. The electronic structure of LSMO is governed by a metal-insulator transition, which is controlled by the thickness of the units and the sample temperature, resulting in a systematic downward band shift for metallic samples (i.e., thick LSMO units, low temperature). We present a systematic study of the changes in the valence-band structure and screening features in Mn
2
p
and Cu
2
p
core-level spectra. The results show that hybridization of Cu
3
d
orbitals with out-of-plane O
2
p
orbitals can be systematically tuned by controlling the band alignment at the interface via the metal-to-insulator transition of the LSMO units. This opens a new route to rational design of functional interfaces and control of orbital reconstructions.
|
Sep 2019
|
|
I09-Surface and Interface Structural Analysis
|
Matthew J.
Wahila
,
Galo
Paez
,
Christopher N.
Singh
,
Anna
Regoutz
,
Shawn
Sallis
,
Mateusz J.
Zuba
,
Jatinkumar
Rana
,
M. Brooks
Tellekamp
,
Jos E.
Boschker
,
Toni
Markurt
,
Jack E. N.
Swallow
,
Leanne A. H.
Jones
,
Tim D.
Veal
,
Wanli
Yang
,
Tien-lin
Lee
,
Fanny
Rodolakis
,
Jerzy T.
Sadowski
,
David
Prendergast
,
Wei-cheng
Lee
,
W. Alan
Doolittle
,
Louis F. J.
Piper
Diamond Proposal Number(s):
[20647, 21430]
Abstract: The metal-insulator transition of
NbO
2
is thought to be important for the functioning of recent niobium oxide-based memristor devices, and is often described as a Mott transition in these contexts. However, the actual transition mechanism remains unclear, as current devices actually employ electroformed
NbO
x
that may be inherently different to crystalline
NbO
2
. We report on our synchrotron x-ray spectroscopy and density-functional-theory study of crystalline, epitaxial
NbO
2
thin films grown by pulsed laser deposition and molecular beam epitaxy across the metal-insulator transition at
∼
810
∘
C
. The observed spectral changes reveal a second-order Peierls transition driven by a weakening of Nb dimerization without significant electron correlations, further supported by our density-functional-theory modeling. Our findings indicate that employing crystalline
NbO
2
as an active layer in memristor devices may facilitate analog control of the resistivity, whereby Joule-heating can modulate Nb-Nb dimer distance and consequently control the opening of a pseudogap.
|
Jul 2019
|
|
