I10-Beamline for Advanced Dichroism - scattering
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Y.
Khaydukov
,
G.
Mccafferty
,
A.
Dobrynin
,
A.
Devishvili
,
A.
Vorobiev
,
P,
Bencok
,
R.
Fan
,
P.
Steadman
,
K.
Mcneill
,
M.
Ormston
Abstract: The deposition process of the IrMn3/Co70Fe30 bilayer of antiferromagnet/ferromagnet (AF/FM) type was modified by introducing a nitrogen additive in argon plasma during the magnetron sputtering of the Co70Fe30 layer. This slight modification significantly enhanced the exchange bias energy density and reduced coercivity of an AF/FM bilayer for the AF IrMn layer thickness ranging from 20 to 50 Å. Calculations indicate that the boost in exchange bias energy density and the reduction in coercivity can be attributed to the increased anisotropy energy of the AF layer, resulting in more effective pinning of the FM layer by AF grains. The increase in anisotropy is caused by the diffusion of nitrogen from the FM into the AF layer, as established by x-ray diffraction, neutron reflectometry, and x-ray magnetic circular dichroism. Our research allows us to improve magnetic characteristics of exchange-coupled FM/AF structures through minor modifications in the sputtering process and/or save up to 20% of the costly IrMn3 target by reducing the thickness of the AF layer.
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Jun 2025
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I09-Surface and Interface Structural Analysis
I10-Beamline for Advanced Dichroism - scattering
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Naina
Kushwaha
,
Olivia
Armitage
,
Brendan
Edwards
,
Liam
Trzaska
,
Jennifer
Rigden
,
Peter
Bencok
,
Deepnarayan
Biswas
,
Tien-Lin
Lee
,
Charlotte
Sanders
,
Gerrit
Van Der Laan
,
Peter
Wahl
,
Phil D. C.
King
,
Akhil
Rajan
Diamond Proposal Number(s):
[33239, 38049]
Open Access
Abstract: Chromium ditelluride, CrTe2, is an attractive candidate van der Waals material for hosting 2D magnetism. However, how the room-temperature ferromagnetism of the bulk evolves as the sample is thinned to the single-layer limit has proved controversial. This, in part, reflects its metastable nature, vs. a series of more stable self-intercalation compounds with higher relative Cr:Te stoichiometry. Here, exploiting a recently developed method for enhancing nucleation in molecular-beam epitaxy growth of transition-metal chalcogenides, we demonstrate the selective stabilisation of high-coverage CrTe2 and Cr2+εTe3 epitaxial monolayers. Combining X-ray magnetic circular dichroism, scanning tunnelling microscopy, and temperature-dependent angle-resolved photoemission, we demonstrate that both compounds order magnetically with a similar TC. We find, however, that monolayer CrTe2 forms as an antiferromagnetic metal, while monolayer Cr2+εTe3 hosts an intrinsic ferromagnetic semiconducting state. This work thus demonstrates that control over the self-intercalation of metastable Cr-based chalcogenides provides a powerful route for tuning both their metallicity and magnetic structure, establishing the CrxTey system as a flexible materials class for future 2D spintronics.
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May 2025
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B18-Core EXAFS
I10-Beamline for Advanced Dichroism - scattering
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Diamond Proposal Number(s):
[34857, 35250]
Open Access
Abstract: Molecular cerium complexes are of interest due to their remarkable redox and photophysical properties. We have investigated the ligand tunability of the electronic structure and properties of cerium(IV) complexes with functionalized tetradentate N2O2-donor ligands: [CeIV(LtBu)2] (1), [CeIV(LH)2] (2) and [CeIV(LNO2)2] (3), where H2LtBu = bis(2-hydroxy-3,5-di-tert-butylbenzyl)(2-pyridylmethyl)amine, H2LH = bis(2-hydroxybenzyl)(2-pyridylmethyl)amine and H2LNO2 = bis(2-hydroxy-5-nitrobenzyl)(2-pyridylmethyl)amine. These compounds all exhibit a quasi-reversible one-electron reduction to cerium(III), with the redox potential correlating with the electron donor–acceptor characteristics of the ligand substituents. This correlation is rationalized by energy stabilization of the HOMO, as determined by density functional theory calculations, and is consistent with arene π → Ce 4f* ligand-to-metal charge transfer bands. The L3-edge XANES exhibits minimal variation in Ce 4f occupation for the three compounds, which suggests that the 4f covalent character and composition of the ground-state character do not vary significantly across the series. However, M4,5-edge XAS shows charge transfer satellites that subtly differ in shape and energy, indicating small distinctions in ligand-to-metal charge transfer for the compounds, consistent with small differences in temperature-independent magnetism. The ability to modulate the redox and optical properties of cerium complexes through ligand derivatization highlights the potential for customizable molecular cerium catalysts and photocatalysts.
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Mar 2025
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I10-Beamline for Advanced Dichroism - scattering
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Abstract: Depth resolved characterization of structural and magnetic profiles of antiferromagnetic/ferromagnetic (AFM/FM) system upon annealing was performed in this work. We studied systems comprising of AFM IrMn
and FM (Co, Fe, Co70Fe30) bilayer structures using magnetometry, polarized neutron reflectometry, soft X-ray magnetic circular dichroism and secondary neutral spectrometry. Structural depth profiles obtained from neutron reflectometry indicate non-homogeneity of the AFM layer even before annealing, which is associated with the migration of manganese to the surface of the sample. Annealing of samples with CoFe and Co layers leads to a slight increase (
5 %) in the migration of manganese, which, however, does not lead to significant degradation of the exchange coupling at the AFM/FM interface. A significantly different picture was observed in the Fe/IrMn
systems where a strong migration of iron into the AFM layer was observed upon annealing of the sample, leading to erosion of the magnetic profile, the formation of a non-magnetic alloy and degradation of the pinning strength. This study can be useful in the optimization of AFM/FM systems in different spintronics devices, including HDD read heads, where thermal annealing is applied at different stages of the device manufacturing process.
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Jan 2025
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B18-Core EXAFS
I10-Beamline for Advanced Dichroism - scattering
I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[34243]
Open Access
Abstract: The increased capacity offered by oxygen-redox active cathode materials for rechargeable lithium- and sodium-ion batteries (LIBs and NIBs, respectively) offers a pathway to the next generation of high-gravimetric-capacity cathodes for use in devices, transportation and on the grid. Many of these materials, however, are plagued with voltage fade, voltage hysteresis and O2 loss, the origins of which can be traced back to changes in their electronic and chemical structures on cycling. Developing a detailed understanding of these changes is critical to mitigating these cathodes’ poor performance. In this work, we present an analysis of the redox mechanism of P2–Na0.67[Mg0.28Mn0.72]O2, a layered NIB cathode whose high capacity has previously been attributed to trapped O2 molecules. We examine a variety of charge compensation scenarios, calculate their corresponding densities of states and spectroscopic properties, and systematically compare the results to experimental data: 25Mg and 17O nuclear magnetic resonance (NMR) spectroscopy, operando X-band and ex situ high-frequency electron paramagnetic resonance (EPR), ex situ magnetometry, and O and Mn K-edge X-ray Absorption Spectroscopy (XAS) and X-ray Absorption Near Edge Spectroscopy (XANES). Via a process of elimination, we suggest that the mechanism for O redox in this material is dominated by a process that involves the formation of strongly antiferromagnetic, delocalized Mn–O states which form after Mg2+ migration at high voltages. Our results primarily rely on noninvasive techniques that are vital to understanding the electronic structure of metastable cycled cathode samples.
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Sep 2024
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B07-B1-Versatile Soft X-ray beamline: High Throughput ES1
I10-Beamline for Advanced Dichroism - scattering
I20-Scanning-X-ray spectroscopy (XAS/XES)
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Lijin
An
,
Ruomu
Zhang
,
Prvanin N.
Didwal
,
Michael W.
Fraser
,
Leanne A. H.
Jones
,
Conor M. E.
Phelan
,
Namrata
Ramesh
,
Grant
Harris
,
Robert S.
Weatherup
,
Jack E. N.
Swallow
,
Peixi
Cong
,
Andrey
Poletayev
,
Erik
Bjorklund
,
Christophe J.
Sahle
,
Pilar
Ferrer
,
David C.
Grinter
,
Peter
Bencok
,
Shusaku
Hayama
,
Saiful
Islam
,
Robert
House
,
Peter D.
Nellist
,
Robert J.
Green
,
Rebecca J.
Nicholls
Diamond Proposal Number(s):
[33283, 33062, 32010]
Open Access
Abstract: Ni-rich layered oxide cathodes can deliver higher energy density batteries, but uncertainties remain over their charge compensation mechanisms and the degradation processes that limit cycle life. Trapped molecular O2 has been identified within LiNiO2 at high states of charge, as seen for Li-rich cathodes where excess capacity is associated with reversible O-redox. Here we show that bulk redox in LiNiO2 occurs by Ni-O rehybridization, lowering the electron density on O sites, but importantly without the involvement of molecular O2. Instead, trapped O2 is related to degradation at surfaces in contact with the electrolyte, and is accompanied by Ni reduction. O2 is removed on discharge, but excess Ni2+ persists forming a reduced surface layer, associated with impeded Li transport. This implicates the instability of delithiated LiNiO2 in contact with the electrolyte in surface degradation through O2 formation and Ni reduction, highlighting the importance of surface stabilisation strategies in suppressing LNO degradation.
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Sep 2024
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B07-B1-Versatile Soft X-ray beamline: High Throughput ES1
I10-Beamline for Advanced Dichroism - scattering
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Diamond Proposal Number(s):
[33639, 34919, 36558]
Open Access
Abstract: Spinel ferrites exhibit significant promise in photocatalysis and other applications due to their compositional diversity and favourable electronic structure, magnetism, and partially tuneable cation distribution. However, their complex properties, for example, the different behaviour of bulk and nanostructured materials, are not well understood. Here, we combine advanced computational and experimental methods with reactivity measurements to explore the inversion degrees, electronic structures, and photocatalytic activities of MFe2O4 spinels (M = Co, Cu, Zn). X-ray diffraction and anomalous X-ray scattering measurements determined bulk inversion degrees of 0.81, 0.91, and 0.26 for CoFe2O4, CuFe2O4, and ZnFe2O4, respectively. Photocatalytic tests showed that only ZnFe2O4 is active in the oxygen evolution reaction (OER), which correlates with its favourable band alignment, as determined through electronic structure simulations. Surface-sensitive X-ray Absorption Spectroscopy (XAS) measurements provided insights into the cation distributions at the surfaces, showing significant deviations from bulk properties, particularly in ZnFe2O4 in which 52% of the near-surface tetrahedral sites are occupied by Fe cations, compared to 26% in the bulk. DFT simulations of ZnFe2O4 illustrated how the surface terminations can alter the thermodynamic preference for cation distribution in comparison with the bulk. Our findings illustrate the complex interplay between surface and bulk properties in spinel ferrites.
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Sep 2024
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I10-Beamline for Advanced Dichroism - scattering
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Open Access
Abstract: Calculations and measurements of polarization-dependent soft X-ray scattering intensity are presented during a magnetic hysteresis cycle. It is confirmed that the dependence of the intensity on the magnetic moment can be linear, quadratic or a combination of both, depending on the polarization of the incident X-ray beam and the direction of the magnetic moment. With a linearly polarized beam, the scattered intensity will have a purely quadratic dependence on the magnetic moment when the magnetic moment is parallel to the scattering plane. However, with the magnetic moment perpendicular to the scattering plane, there is also a linear component. This means that, when measuring the hysteresis with linear polarization during a hysteresis cycle, the intensity will be an even function of the applied field when the change in the magnetic moment (and field) is confined within the scattering plane but becomes more complicated when the magnetic moment is out of the scattering plane. Furthermore, with circular polarization, the dependence of the scattered intensity on the moment is a combination of linear and quadratic. With the moment parallel to the scattering plane, the linear component changes with the helicity of the incident beam. Surprisingly, in stark contrast to absorption studies, even when the magnetic moment is perpendicular to the scattering plane there is still a dependence on the moment with a linear component. This linear component is completely independent of the helicity of the beam, meaning that the hysteresis loops will not be inverted with helicity.
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May 2024
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I10-Beamline for Advanced Dichroism - scattering
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Diamond Proposal Number(s):
[21117, 23982]
Open Access
Abstract: The mixing valence d and s orbitals are predicted to strongly influence the electronic structure of linearly coordinated molecules, including transition metals, lanthanides and actinides. In specific cases, novel magnetic properties, such as single-ion magnetic coercivity or long spin decoherence times, ensue. Inspired by how the local coordination symmetry can engender such novel phenomena, in this study, we focus our attention on dopants (Mn, Fe, Co, Ni, Cu) in lithium nitride to accept innovation from molecular magnetism in a high symmetry P6/mmm solid-state crystal. The linear coordination environment results in strong 3d-4s mixing, proving to be an ideal series to investigate the role of d-s mixing and bonding on electronic structure and magnetism. It is shown that L2,3-edge XAS can be applied to experimentally identify the presence of 3d-4s mixing and the influence this has on ligand-field splitting. XMCD specifies how spin-orbit coupling is affected. The combined spectroscopies are analysed to determine the effect of 4s mixing with support from ab initio calculations. The results provide new insight of relevance to future applications, including quantum information processing and the sustainable replacement of rare earths in magnets.
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Dec 2023
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I05-ARPES
I10-Beamline for Advanced Dichroism - scattering
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Gesa-R.
Siemann
,
Seo-Jin
Kim
,
Edgar
Abarca Morales
,
Philip A. E.
Murgatroyd
,
Andela
Zivanovic
,
Brendan
Edwards
,
Igor
Markovic
,
Federico
Mazzola
,
Liam
Trzaska
,
Oliver J.
Clark
,
Chiara
Bigi
,
Haijing
Zhang
,
Barat
Achinuq
,
Thorsten
Hesjedal
,
Matthew D.
Watson
,
Timur K.
Kim
,
Peter
Bencok
,
Gerrit
Van Der Laan
,
Craig M.
Polley
,
Mats
Leandersson
,
Hanna
Fedderwitz
,
Khadiza
Ali
,
Thiagarajan
Balasubramanian
,
Marcus
Schmidt
,
Michael
Baenitz
,
Helge
Rosner
,
Phil D. C.
King
Diamond Proposal Number(s):
[28412, 31035]
Open Access
Abstract: In half-metallic systems, electronic conduction is mediated by a single spin species, offering enormous potential for spintronic devices. Here, using microscopic-area angle-resolved photoemission, we show that a spin-polarised two-dimensional hole gas is naturally realised in the polar magnetic semiconductor AgCrSe2 by an intrinsic self-doping at its CrSe2-terminated surface. Through comparison with first-principles calculations, we unveil a striking role of spin-orbit coupling for the surface hole gas, unlocked by both bulk and surface inversion symmetry breaking, suggesting routes for stabilising complex magnetic textures in the surface layer of AgCrSe2.
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Oct 2023
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