I09-Surface and Interface Structural Analysis
|
Diamond Proposal Number(s):
[28680]
Open Access
Abstract: SrTiO3 (STO) is an incipient ferroelectric perovskite oxide for which the onset of ferroelectric order is suppressed by quantum fluctuations. This property results in a very large increase in static dielectric constant from ∼300 at room temperature to ∼20,000 at liquid He temperature in bulk single crystals. However, the low-temperature dielectric constant of epitaxial STO films is typically a few hundred to a few thousand. Here, we use all-epitaxial capacitors of the form n-STO/undoped STO/n-STO (001) prepared by hybrid molecular beam epitaxy, to demonstrate intrinsic dielectric constants of an unstrained STO (001) film exceeding 25,000. We show that the n-STO/undoped STO interface plays a critically important role not previously considered in determining the dielectric properties that must be properly accounted for to determine the intrinsic dielectric constant.
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Jun 2022
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I07-Surface & interface diffraction
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Diamond Proposal Number(s):
[8225, 8733]
Open Access
Abstract: Exposure to the secondary pollutant ozone in ambient air is associated with adverse health effects when inhaled. In this work we use surface pressure measurements, combined with X-ray and neutron reflection, to observe changes in a layer of lung surfactant at the air water interface when exposed to gas phase ozone. The results demonstrate that the layer reacts with ozone changing its physical characteristics. A slight loss of material, a significant thinning of the layer and increased hydration of the surfactant material is observed. The results support the hypothesis that unsaturated lipids present in lung surfactant are still susceptible to rapid reaction with ozone and the reaction changes the properties of the interfacial layer.
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Jun 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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I10-Beamline for Advanced Dichroism
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Diamond Proposal Number(s):
[19173]
Abstract: We present an investigation on the structural and magnetic properties of the interfaces of
Fe
3
O
4
/
MgO
(
001
)
and
Fe
3
O
4
/
NiO
/
MgO
(
001
)
by extracting cation-selective magneto-optical depth profiles by means of x-ray resonant magnetic reflectivity in combination with charge-transfer multiplet simulations of x-ray magnetic circular dichroism data. For
Fe
3
O
4
/
MgO
(
001
)
, the magneto-optical depth profiles at the
Fe
2
+
oct
and the
Fe
3
+
oct
resonant energies follow exactly the structural profile, while the magneto-optical depth profile at the
Fe
3
+
tet
resonance is offset by
3.2
±
1.3
Å from the interface, consistent with a
B
-site interface termination of
Fe
3
O
4
with fully intact magnetic order. In contrast, for
Fe
3
O
4
/
NiO
(
001
)
, the magneto-optical depth profiles at the
Fe
2
+
oct
and the
Ni
2
+
resonances agree with the structural profile, but the interface positions of the magneto-optical depth profiles at the
Fe
3
+
oct
and the
Fe
3
+
tet
resonances are spatially shifted by
3.3
±
1.4
and
2.7
±
0.9
Å, respectively, not consistent with a magnetically ordered stoichiometric interface. This may be related to an intermixed
(
Ni
,
Fe
)
O
layer at the interface. The dichroic depth profile at the Ni
L
3
edge might hint at uncompensated magnetic moments throughout the NiO film.
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Jun 2022
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I09-Surface and Interface Structural Analysis
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Le
Wang
,
Zhenzhong
Yang
,
Widitha S.
Samarakoon
,
Yadong
Zhou
,
Mark E.
Bowden
,
Hua
Zhou
,
Jinhui
Tao
,
Zihua
Zhu
,
Nabajit
Lahiri
,
Timothy C.
Droubay
,
Zachary W.
Lebens-Higgins
,
Xinmao
Yin
,
Chi Sin
Tang
,
Zhenxing
Feng
,
Louis F. J.
Piper
,
Andrew T. S.
Wee
,
Scott A.
Chambers
,
Yingge
Du
Diamond Proposal Number(s):
[19162]
Abstract: Epitaxial growth is a powerful tool for synthesizing heterostructures and integrating multiple functionalities. However, interfacial mixing can readily occur and significantly modify the properties of layered structures, particularly for those containing energy storage materials with smaller cations. Here, we show a two-step sequence involving the growth of an epitaxial LiCoO2 cathode layer followed by the deposition of a binary transition metal oxide. Orientation-controlled epitaxial synthesis of the model solid-state-electrolyte Li2WO4 and anode material Li4Ti5O12 occurs as WO3 and TiO2 nucleate and react with Li ions from the underlying cathode. We demonstrate that this lithiation-assisted epitaxy approach can be used for energy materials discovery and exploring different combinations of epitaxial interfaces that can serve as well-defined model systems for mechanistic studies of energy storage and conversion processes.
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Jun 2022
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I07-Surface & interface diffraction
|
Diamond Proposal Number(s):
[20529]
Abstract: We present a surface-sensitive X-ray scattering study on the influence of gaseous and aerolized perfluorocarbons (FCs) on zwitterionic and anionic phospholipid Langmuir films, which serve as a simplified model system of lung surfactants. It was found that small gaseous FC molecules like F-propane and F-butane penetrate phospholipid monolayers and accumulate between the alkyl chains and form islands. This clustering process can trigger the formation of lipid crystallites at low initial surface pressures. In contrast, the large linear FC F-octyl bromide fluidizes membranes, causing a dissolution of crystalline domains. The bicyclic FC F-decalin accumulates between the alkyl chains of 1,2-dipalmitoyl phosphatidylcholine but cannot penetrate the more densely packed 1,2-dipalmitoyl phosphatidic acid films because of its size. The effects of FCs on lung surfactants are discussed in the framework of currently proposed therapeutic methods for acute respiratory distress syndrome using FC gases, vapor, or aerosol ventilation causing monolayer fluidization effects. This study implies that the highly biocompatible and nontoxic FCs could be beneficial in the treatment of lung diseases with injured nonfunctional lung surfactants in a novel approach for ventilation.
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May 2022
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B18-Core EXAFS
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Diamond Proposal Number(s):
[14239]
Open Access
Abstract: Garnet solid electrolytes, of the form Li7La3Zr2O12 (LLZO), remain an enticing prospect for solid-state batteries owing to their chemical and electrochemical stability in contact with metallic lithium. Dopants, often employed to stabilize the fast ion conducting cubic garnet phase, typically have no effect on the chemical stability of LLZO in contact with Li metal but have been found recently to impact the properties of the Li/garnet interface. For dopants more “reducible” than Zr (e.g., Nb and Ti), contradictory reports of either raised or reduced Li/garnet interfacial resistances have been attributed to the dopant. Here, we investigate the Li/LLZO interface in W-doped Li7La3Zr2O12 (LLZWO) to determine the influence of a “reducible” dopant on the electrochemical properties of the Li/garnet interface. Single-phase LLZWO is synthesized by a new sol–gel approach and densified by spark plasma sintering. Interrogating the resulting Li/LLZWO interface/interphase by impedance, muon spin relaxation and X-ray absorption spectroscopies uncover the significant impact of surface lithiation on electrochemical performance. Upon initial contact, an interfacial reaction occurs between LLZWO and Li metal, leading to the reduction of surface W6+ centers and an initial reduction of the Li/garnet interfacial resistance. Propagation of this surface reaction, driven by the high mobility of Li+ ions through the grain surfaces, thickens the resistive interphases throughout the material and impedes Li+ ion transport between the grains. The resulting high resistance accumulating in the system impedes cycling at high current densities. These insights shed light on the nature of lithiated interfaces in garnet solid electrolytes containing a reducible dopant where high Li+ ion mobility and the reducible nature of the dopant can significantly affect electrochemical performance.
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May 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
|
Diamond Proposal Number(s):
[23730]
Open Access
Abstract: A thermally induced order–disorder transition of tetraphenylporphyrin (2H-TPP) on Au(111) is characterised by scanning probe microscopy and X-ray photoelectron spectroscopy-based techniques. We observed that a transition from an ordered close-packed phase to a disordered diffuse phase is correlated with an on-surface cyclodehydrogenation reaction, and that additional heating of this diffuse phase gives rise to a single distinct nitrogen environment indicative of the formation of a Au–TPP species.
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May 2022
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B07-C-Versatile Soft X-ray beamline: Ambient Pressure XPS and NEXAFS
|
Simon
Astley
,
Di
Hu
,
Kerry
Hazeldine
,
Johnathan
Ash
,
Rachel E.
Cross
,
Simon
Cooil
,
Martin W.
Allen
,
James
Evans
,
Kelvin
James
,
Federica
Venturini
,
David C.
Grinter
,
Pilar
Ferrer
,
Rosa
Arrigo
,
Georg
Held
,
Gruffudd T.
Williams
,
D. Andrew
Evans
Diamond Proposal Number(s):
[18182]
Open Access
Abstract: Photoelectron spectroscopy is a powerful characterisation tool for semiconductor surfaces and interfaces, providing in principle a correlation between the electronic band structure and surface chemistry along with quantitative parameters such as the electron affinity, interface potential, band bending and band offsets. However, measurements are often limited to ultrahigh vacuum and only the top few atomic layers are probed. The technique is seldom applied as an in situ probe of surface processing; information is usually provided before and after processing in a separate environment, leading to a reduction in reproducibility. Advances in instrumentation, in particular electron detection has enabled these limitations to be addressed, for example allowing measurement at near-ambient pressures and the in situ, real-time monitoring of surface processing and interface formation. A further limitation is the influence of the measurement method through irreversible chemical effects such as radiation damage during X-ray exposure and reversible physical effects such as the charging of low conductivity materials. For wide-gap semiconductors such as oxides and carbon-based materials, these effects can be compounded and severe. Here we show how real-time and near-ambient pressure photoelectron spectroscopy can be applied to identify and quantify these effects, using a gold alloy, gallium oxide and semiconducting diamond as examples. A small binding energy change due to thermal expansion is followed in real-time for the alloy while the two semiconductors show larger temperature-induced changes in binding energy that, although superficially similar, are identified as having different and multiple origins, related to surface oxygen bonding, surface band-bending and a room-temperature surface photovoltage. The latter affects the p-type diamond at temperatures up to 400 °C when exposed to X-ray, UV and synchrotron radiation and under UHV and 1 mbar of O2. Real-time monitoring and near-ambient pressure measurement with different excitation sources has been used to identify the mechanisms behind the observed changes in spectral parameters that are different for each of the three materials. Corrected binding energy values aid the completion of the energy band diagrams for these wide-gap semiconductors and provide protocols for surface processing to engineer key surface and interface parameters.
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May 2022
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