B07-B1-Versatile Soft X-ray beamline: High Throughput ES1
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Diamond Proposal Number(s):
[34919, 37955]
Open Access
Abstract: A combination of experimental methods and computational techniques have been used to investigate the composition of the zinc ferrite (ZnFe2O4) (1 1 1) single crystal surface under different preparation methods. Surface-sensitive XPS and NEXAFS measurements show that upon annealing in ultra-high vacuum (UHV), Zn depletion occurs, leading to the formation of an iron-rich (1 1 1) surface, whereas annealing in the presence of O2 gas maintains a more bulk-like ZnFe2O4 surface composition. Analysis of the Fe 2p photoemission (XPS) and Fe L edge X-ray absorption signals shows a clear difference in iron oxidation state and distribution between the two different preparation conditions. After annealing in UHV, a mixed Fe2+/Fe3+ oxidation state and a cation distribution like that of a magnetite (Fe3O4) structure is observed, whereas after annealing in oxygen gas only Fe3+, mostly in octahedral coordination, is observed, as expected for a ZnFe2O4 structure. Temperature-dependent XPS confirms significant Zn depletion in the near-surface region above 500 °C under UHV, with almost no Zn remaining at 600 °C; under an O2 atmosphere no zinc depletion is observed up to 600 °C. A theoretical model based on DFT simulations illustrates how reduction from ZnFe2O4 to Fe3O4 with formation of O2 and Zn gas is thermodynamically feasible under UHV conditions, whereas the same reaction is not favourable at higher oxygen partial pressures. Our findings demonstrate the strong impact that UHV treatment has on zinc ferrite surfaces, and cautions that UHV environments, routinely employed for surface analysis, can themselves induce substantial modifications to the surface, thereby complicating the interpretation of measurements in the context of catalytically relevant conditions.
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Dec 2025
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I09-Surface and Interface Structural Analysis
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Diamond Proposal Number(s):
[29113]
Open Access
Abstract: LiNi0.5Mn1.5O4 (LNMO) cathodes offer a cobalt-free, high-voltage alternative to current state-of-the-art Li-ion battery cathodes, and are particularly well-suited for high-power applications due to their 3D lithium-ion pathways and structural stability. However, degradation of commercial electrolytes at high voltages exacerbates capacity decay, as instability at the cathode surface causes active material loss, surface reconstructions, thickening surface layers, and increases in internal cell resistance. Cationic substitution has been proposed to enhance surface stability, thus limiting capacity decay. Here, we demonstrate the stabilizing effect of Mg on the LNMO cathode surface, which is most evident during the early stages of cycling. This study indicates that improved O 2p-TM 3d hybridization in Mg-substituted LNMO, facilitated by Li-site defects, leads to the formation of a stable surface layer that is corrosion-resistant at high voltage. Examination of Fe-substituted and unsubstituted LNMO further confirms that the surface stability is uniquely enabled by Mg substitution. This work offers valuable insights into surface design for reducing degradation in high-voltage spinel cathodes.
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Nov 2025
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I09-Surface and Interface Structural Analysis
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Sarah May
Sibug-Torres
,
Marika
Niihori
,
Elle
Wyatt
,
Rakesh
Arul
,
Nicolas
Spiesshofer
,
Tabitha
Jones
,
Duncan
Graham
,
Bart
De Nijs
,
Oren A.
Scherman
,
Reshma R.
Rao
,
Mary P.
Ryan
,
Alexander
Squires
,
Christopher N.
Savory
,
David O.
Scanlon
,
Abdalghani
Daaoub
,
Sara
Sangtarash
,
Hatef
Sadeghi
,
Jeremy J.
Baumberg
Diamond Proposal Number(s):
[34784]
Open Access
Abstract: Controlling surface chemistry at the nanoscale is essential for stabilizing structure and tuning function in plasmonic, catalytic and sensing systems, where even trace ligands or ions can reshape surface charge and reactivity. However, probing such dynamic interfaces under operando conditions remains challenging, limiting efforts to engineer nanomaterials with precision. Here, using in situ surface-enhanced Raman spectroscopy, we identify a transient Au–Cl adlayer that forms during electrochemical cycling at gold interfaces. The adlayer exhibits significant charge transfer between gold and chlorine, generating an outward-facing dipole that polarizes neighbouring atoms and modulates the local potential. This dipole stabilizes nanogap interfaces and directs oriented ligand rebinding, enabling reversible reconstruction of subnanometre architectures. It also alters interfacial charge distributions and mediates electron transfer between gold oxidation states, acting as a redox-active intermediate. These findings show how transient surface species shape nanoscale reactivity and stability, offering strategies for designing catalysts, sensors and nanomaterials.
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Nov 2025
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I09-Surface and Interface Structural Analysis
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Wenjing
Xu
,
Hailing
Guo
,
Zhenni
Yang
,
Yihong
Chen
,
Xiangyu
Xu
,
Tien-Lin
Lee
,
Duanyang
Chen
,
Xinxin
Yu
,
Yuzheng
Guo
,
Zhaofu
Zhang
,
Hongji
Qi
,
Kelvin H. I.
Zhang
Diamond Proposal Number(s):
[37428]
Abstract: In this work, we investigate the electronic structure and interfacial band alignment of β-(Al𝑥Ga1−𝑥)2O3/Ga2O3 heterojunctions using a combination of synchrotron-based hard x-ray photoemission spectroscopy (HAXPES) and first-principles hybrid density functional theory calculations. β-(Al𝑥Ga1−𝑥)2O3 films with Al compositions of x = 0.12, 0.19, and 0.29 were grown on Fe-doped β-Ga2O3 (010) substrates via pulsed laser deposition. The band gap of β-(Al𝑥Ga1−𝑥)2O3 increases from (4.83 ± 0.05) eV (x = 0) to (5.37 ± 0.08) eV (x = 0.29), primarily driven by an upward shift of the conduction band edge due to hybridization between Al 3s and Ga 4s states, while the valence band edge exhibits a slight downward shift. Both experimental HAXPES data and theoretical calculations confirmed the formation of a “type I” (straddling) band alignment in the β-(Al𝑥Ga1−𝑥)2O3/Ga2O3 heterojunctions. For instance, at x = 0.29, the conduction band offset and valence band offset are approximately 0.33 and 0.21 eV, respectively. These findings provide valuable insights for designing modulation-doped β-(Al𝑥Ga1−𝑥)2O3/Ga2O3 heterostructures, enabling the realization of a two-dimensional electron gas and its application in high-frequency electronic devices.
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Oct 2025
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I09-Surface and Interface Structural Analysis
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Diamond Proposal Number(s):
[25807]
Open Access
Abstract: The solid electrolyte interphase that forms on Li6PS5Cl argyrodite solid electrolytes has been reported to continually grow through a diffusion-controlled process, yet this process is not fully understood. Here, we use a combination of electrochemical and X-ray photoelectron spectroscopy techniques to elucidate the role of phosphorus in this growth mechanism. We uncover how Li6PS5Cl can decompose at potentials well above the full reduction to Li3P, forming partially lithiated phosphorus species, LixP. We provide evidence of a gradient of LixP species throughout the solid electrolyte interphase and propose a growth mechanism in which the rate-determining step is the diffusion of lithium through LixP. We predict continuous solid electrolyte interphase growth as long as metallic lithium is present and a LixP percolation pathway exists, highlighting the importance of understanding and engineering solid electrolyte interphase composition and nanostructure in solid-state batteries. We believe that this growth mechanism would apply to any solid electrolyte interphase that can contain partially lithiated phosphorus, or potentially any lithium alloy.
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Oct 2025
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I09-Surface and Interface Structural Analysis
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Ali
Sufyan
,
Tyler
James
,
Connor
Fields
,
Shabnam
Naseri
,
Filipe L. Q.
Junqueira
,
Sofia
Alonso Perez
,
Sally
Bloodworth
,
Gabriella
Hoffman
,
Mark C.
Walkey
,
Elizabeth S.
Marsden
,
Richard J.
Whitby
,
Yitao
Wang
,
David A.
Duncan
,
Tien-Lin
Lee
,
James N.
O'Shea
,
Andreas
Larsson
,
Brian
Kiraly
,
Philip
Moriarty
Diamond Proposal Number(s):
[31574]
Open Access
Abstract: Core-level and tunnelling spectroscopies applied to noble gas endofullerenes offer complementary insights into electron transfer rates, addressing both intramolecular and extramolecular processes. Elastic and inelastic tunnelling spectroscopy of empty C60 and Kr@C60 on Pb/Cu(111) each show that the encapsulated atom is essentially invisible to scanning probes. We interpret the lineshape of the lowest unoccupied molecular orbital (LUMO) of Pb-adsorbed (endo)fullerenes in tunnelling spectra as a signature of the dynamic Jahn-Teller (DJ-T) effect. This effect persists in electronically decoupled second-layer molecules, which also display distinct vibronic progressions in on-resonance tunnelling. DFT calculations reproduce the LUMO alignment and low density of states at the Fermi level seen in experimental tunnelling spectra for (endo)fullerenes on Pb, and, in line with submolecular resolution STM images, also predict that an atom-down orientation of the fullerene cage is energetically most favourable (although other adsorption geometries differ only by tens of meV at most). In contrast to the tunnelling data, core-level-focussed techniques -namely, photoemission, X-ray absorption, and resonant Auger-Meitner electron spectroscopy -of Ar@C60/Pb(111) indicate that the encapsulated atom is heavily coupled to the molecular environment, with both a clear influence of substrate screening on the core-level lineshape and the absence of spectator signal in decay spectra.
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Oct 2025
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I09-Surface and Interface Structural Analysis
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Han
Yan
,
Yan
Wang
,
Yang
Li
,
Dibya
Phuyal
,
Lixin
Liu
,
Hailing
Guo
,
Yuzheng
Guo
,
Tien-Lin
Lee
,
Minhyuk
Kim
,
Hu Young
Jeong
,
Manish
Chhowalla
Diamond Proposal Number(s):
[30105, 33391, 32963, 38086]
Open Access
Abstract: Two-dimensional transition metal dichalcogenide semiconductors possess ideal attributes for meeting industry scaling targets for transistor channel technology. However, the development of scaled field-effect transistors (FETs) requires industry-compatible gate dielectrics with low equivalent oxide thicknesses. Here we show that zirconium oxide (ZrO2)—an industry-compatible high-dielectric-constant (k) oxide—can form a clean interface with two-dimensional molybdenum disulfide (MoS2). Photoelectron spectroscopy analysis shows that although silicon dioxide and hafnium oxide substrates introduce the doping of MoS2, ZrO2 exhibits no measurable interactions with MoS2. Back-gated monolayer MoS2 FETs using ZrO2 as a dielectric exhibit stable and positive threshold voltages of 0.36 V, subthreshold swings of 75 mV dec−1 and ON currents of more than 400 µA. We also use ZrO2 dielectrics to fabricate p-type tungsten diselenide FETs with ON-state currents of more than 200 µA µm−1. Atomic-resolution imaging of ZrO2 deposited on top of MoS2 reveals a defect-free interface, which leads to top-gated FETs with an equivalent oxide thickness of 0.86 nm and subthreshold swing values of 80 mV dec−1. The clean interface between ZrO2 and monolayer MoS2 allows the effective modulation of threshold voltage in top-gated FETs via gate metal work-function engineering.
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Oct 2025
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I09-Surface and Interface Structural Analysis
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Ziqi
Zhang
,
Yan
Wang
,
Zhenni
Yang
,
Wenjing
Xu
,
Yan
Sun
,
Yihong
Chen
,
Xiangyu
Xu
,
Ye
Yang
,
Duanyang
Chen
,
Xin
Dong
,
Hao
Long
,
Hongji
Qi
,
Kelvin H. L.
Zhang
Diamond Proposal Number(s):
[37428]
Open Access
Abstract: In this work, homoepitaxial growth and in-depth study on the electronic structure of Si doped β-Ga2O3 thin films on (100) oriented Fe doped Ga2O3 substrates are reported. Carrier concentrations ranging from 3.7 × 1018 cm−3 to 1.6 × 1020 cm−3 were achieved with Si doping level from 0.01% to 1%. The highest conductivity achieved is 468.8 S/cm, making the films promising ohmic contact electrodes. Synchrotron based hard x-ray photoemission spectroscopy (HAXPES) were used to gain insights into the evolution of electronic structure of the degenerately doped films. The results show that the optical bandgaps of the films increase with Si doping, because of the progressive occupation of the bottom of the conduction band by the electrons, i.e., Burstein-Moss shift (∆BM). On the other hand, doping induced bandgap renormalization (∆BGR) leads to narrowing of the fundamental bandgap. The ∆BGR value is slightly higher than those of (010) oriented films at a similar carrier concentration. The anisotropic nature of β-Ga2O3, including the crystal field splitting and the dielectric constant, was found to contribute to the observed crystal orientation-dependent ∆BGR behavior. By understanding the Burstein-Moss and bandgap renormalization effects, the electronic and optical properties of β-Ga2O3 materials can be optimized for optoelectronic device applications.
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Oct 2025
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I09-Surface and Interface Structural Analysis
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C.-H.
Min
,
M.
Scholz
,
T.-L.
Lee
,
C.
Schlueter
,
A.
Gloskovskii
,
E. D. L.
Rienks
,
V.
Hinkov
,
H.
Bentmann
,
Y. S.
Kwon
,
F.
Reinert
,
H.-D.
Kim
,
K.
Rossnagel
,
S.
Müller
,
W. J.
Choi
,
V.
Zabolotnyy
,
M.
Heber
,
J. D.
Denlinger
,
C.-J.
Kang
,
M.
Kalläne
,
N.
Wind
,
L.
Dudy
Diamond Proposal Number(s):
[22630]
Abstract: Exotic quasiparticle states have been proposed in mixed-valent compounds exhibiting valence transitions. However, clear spectroscopic evidence identifying these states has remained elusive. Using synchrotron-based hard x-ray and extreme ultraviolet photoemission spectroscopy, we have probed the Tm 3𝑑 and 4𝑓 emissions in TmSe1−𝑥Te𝑥, where a Te concentration-dependent semimetal–insulator transition occurs alongside the valence transition. Our photoemission results, which are characteristic of the bulk, track this combined transition across the critical concentration (𝑥𝑐 =0.29). Notably, our results reveal a noninteger valence for the insulating phase and a novel quasiparticle excitation in the semimetallic phase: a Holstein polaron that extends beyond the standard periodic Anderson model.
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Oct 2025
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B07-C-Versatile Soft X-ray beamline: Ambient Pressure XPS and NEXAFS
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Diamond Proposal Number(s):
[33415, 34976]
Open Access
Abstract: Electro-oxidation is one of the most promising and eco-friendly technologies for water decontamination. However, its industrial application is still limited by the high cost, poor faradaic efficiency, low durability, and potential toxicity of common high-power oxidation anodes. These challenges have been addressed by developing a novel composite comprising a mixed metal oxide (NiMnO3) and reduced graphene oxide (rGO). The NiMnO3–rGO anode allowed the fast and complete removal of phenol. Among different highly porous substrates, graphite felt (GF) led to the highest energy efficiency, since the GF/NiMnO3–rGO anode yielded 100% phenol removal within only 30 min at a current density as low as 10 mA cm−2, which was accompanied by 85% COD removal at 120 min. This anode demonstrated excellent stability, maintaining 100% phenol removal efficiency across five consecutive cycles while also showing low energy consumption (60–65 Wh (kg COD)−1). Operando X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) analysis provided mechanistic insights. It is demonstrated that rGO shifts the ˙OH production pathway towards the lattice oxygen mechanism (LOM), in contrast to the adsorbate evolution mechanism (AEM) observed for NiMnO3 alone. This mechanistic shift supports the enhanced stability and sustained electrocatalytic activity, contributing to the high performance of the GF/NiMnO3–rGO composite anode in the context of a more sustainable technology for treating organic contaminants.
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Oct 2025
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