|
|
Abstract: Previous work has documented time‐ and temperature‐dependent variations in the Curie temperature (Tc) of natural titanomagnetites, independent of any changes in sample composition. To better understand the atomic‐scale processes responsible for these variations, we have generated a set of synthetic titanomagnetites with a range of Ti, Mg, and Al substitution; a subset of samples was additionally oxidized at low temperature (150°C). Samples were annealed at temperatures between 325‐400 °C for up to 1000 h and characterized in terms of magnetic properties; Fe valence and site occupancy were constrained by X‐ray magnetic circular dichroism (XMCD) and Mössbauer spectroscopy. Annealing results in large (up to ~100 °C) changes in Tc, but Mössbauer, XMCD, and saturation magnetization data all demonstrate that intersite reordering of Fe2+/Fe3+ does not play a role in the observed Tc changes. Rather, the data are consistent with vacancy‐enhanced nanoscale chemical clustering within the octahedral sublattice. This clustering may be a precursor to chemical unmixing at temperatures below the titanomagnetite binary solvus. Additionally, the data strongly support a model where cation vacancies are predominantly situated on octahedral sites; Mg‐substitution is largely accommodated on octahedral sites; and Al‐substitution is split between the two sites.
|
Apr 2019
|
|
I09-Surface and Interface Structural Analysis
|
Paul C.
Rogge
,
Ravini U.
Chandrasena
,
Antonio
Cammarata
,
Robert J.
Green
,
Padraic
Shafer
,
Benjamin M.
Lefler
,
Amanda
Huon
,
Arian
Arab
,
Elke
Arenholz
,
Ho Nyung
Lee
,
Tien-lin
Lee
,
Slavomir
Nemsak
,
James M.
Rondinelli
,
Alexander
Gray
,
Steven J.
May
Diamond Proposal Number(s):
[17824]
Abstract: We investigated the metal-insulator transition for epitaxial thin films of the perovskite CaFeO3, a material with a significant oxygen ligand hole contribution to its electronic structure. We find that biaxial tensile and compressive strain suppress the metal-insulator transition temperature. By combining hard x-ray photoelectron spectroscopy, soft x-ray absorption spectroscopy, and density functional calculations, we resolve the element-specific changes to the electronic structure across the metal-insulator transition. We demonstrate that the Fe sites undergo no observable spectroscopic change between the metallic and insulating states, whereas the O electronic configuration undergoes significant changes. This strongly supports the bond-disproportionation model of the metal-insulator transition for CaFeO3 and highlights the importance of ligand holes in its electronic structure. By sensitively measuring the ligand hole density, however, we find that it increases by ∼5–10% in the insulating state, which we ascribe to a further localization of electron charge on the Fe sites. These results provide detailed insight into the metal-insulator transition of negative charge transfer compounds and should prove instructive for understanding metal-insulator transitions in other late transition metal compounds such as the nickelates.
|
Jan 2018
|
|
I06-Nanoscience
I10-Beamline for Advanced Dichroism
|
C. J.
Durrant
,
L. R.
Shelford
,
R. A. J.
Valkass
,
R. J.
Hicken
,
A. I.
Figueroa
,
A. A.
Baker
,
G.
Van Der Laan
,
L. B.
Duffy
,
P.
Shafer
,
C.
Klewe
,
E.
Arenholz
,
S. A.
Cavill
,
J. R.
Childress
,
J. A.
Katine
Diamond Proposal Number(s):
[8782, 11585]
Abstract: Spin pumping has been studied within Ta / Ag / Ni81Fe19 (0–5 nm) / Ag (6 nm) / Co2MnGe (5 nm) / Ag / Ta large-area spin-valve structures, and the transverse spin current absorption of Ni81Fe19 sink layers of different thicknesses has been explored. In some circumstances, the spin current absorption can be inferred from the modification of the Co2MnGe source layer damping in vector network analyzer ferromagnetic resonance (VNAFMR)
experiments. However, the spin current absorption is more accurately determined from element-specific phase-resolved x-ray ferromagnetic resonance (XFMR) measurements that directly probe the spin transfer torque (STT) acting on the sink layer at the source layer resonance. Comparison with a macrospin model allows the real part of the effective spin mixing conductance to be extracted. We find that spin current absorption in the outer Ta layers has a significant impact, while sink layers with thicknesses of less than 0.6 nm are found to be discontinuous and super-paramagnetic at room temperature, and lead to a noticeable increase of the source layer damping. For the thickest 5-nm sink layer, increased spin current absorption is found to coincide with a reduction of the zero frequency FMR line width that we attribute to improved interface quality. This study shows that the transverse spin current absorption does not follow a universal dependence upon sink layer thickness but instead the structural quality of the sink layer plays a crucial role.
|
Oct 2017
|
|
|
|
J.
Li
,
L. R.
Shelford
,
P.
Shafer
,
A.
Tan
,
J. X.
Deng
,
P. S.
Keatley
,
C.
Hwang
,
E.
Arenholz
,
G.
Van Der Laan
,
R. J.
Hicken
,
Z. Q.
Qiu
Abstract: Despite recent progress in spin-current research, the detection of spin current has mostly remained indirect. By synchronizing a microwave waveform with synchrotron x-ray pulses, we use the ferromagnetic resonance of the Py (Ni 81 Fe 19 ) layer in a Py/Cu/Cu 75 Mn 25 /Cu/Co multilayer to pump a pure ac spin current into the Cu 75 Mn 25 and Co layers, and then directly probe the spin current within the Cu 75 Mn 25 layer and the spin dynamics of the Co layer by x-ray magnetic circular dichroism. This element-resolved pump-probe measurement unambiguously identifies the ac spin current in the Cu 75 Mn 25 layer.
|
Aug 2016
|
|
|
|
James
Byrne
,
Victoria
Coker
,
Eva
Cespedes
,
Paul L.
Wincott
,
David J.
Vaughan
,
Richard
Pattrick
,
Gerrit
Van Der Laan
,
Elke
Arenholz
,
Floriana
Tuna
,
Martin
Bencsik
,
Jonathan R.
Lloyd
,
Neil
Telling
Abstract: The magnetic moments of magnetite nanoparticles are dramatically enhanced through the addition of zinc in a microbiologically driven synthesis procedure. The particles are produced through the reduction of Fe(III)-compounds containing Zn(II) by the iron reducing bacterium Geobacter sulfurreducens .
Results indicate a signifi cant increase in the saturation magnetization by over 50% compared to magnetite at both room and low temperatures for relatively minor quantities of zinc substitution. A maximum saturation magnetization of nearly 100 emu g −1 of sample is measured at room temperature. Analysis of the cation site ordering reveals a complex dependence on the Zn content, with the combined effect of Zn substitution of Fe 3+ ions on tetrahedral sites, together with Fe 2+ cation oxidation, leading to the observed magnetization enhancement for low Zn doping levels. The improved magnetic properties give superior performance in MRI applications with an MRI contrast enhancement among the largest values reported, being more than 5 times larger than a commercial contrast agent (Feridex) measured under identical conditions.The synthesis technique applied here involves an environmentally benign route and offers the potential to tune the magnetic properties of magnetic
nanoparticles, with increased overall magnetization desirable for many different commercial applications.
|
May 2014
|
|
I10-Beamline for Advanced Dichroism
|
Open Access
Abstract: For decades, a link between increased levels of iron and areas of Alzheimer's disease (AD) pathology has been recognized, including AD lesions comprised of the peptide β-amyloid (Aβ). Despite many observations of this association, the relationship between Aβ and iron is poorly understood. Using X-ray microspectroscopy, X-ray absorption spectroscopy, electron microscopy and spectrophotometric iron(II) quantification techniques, we examine the interaction between Aβ(1–42) and synthetic iron(III), reminiscent of ferric iron stores in the brain. We report Aβ to be capable of accumulating iron(III) within amyloid aggregates, with this process resulting in Aβ-mediated reduction of iron(III) to a redox-active iron(II) phase. Additionally, we show that the presence of aluminium increases the reductive capacity of Aβ, enabling the redox cycling of the iron. These results demonstrate the ability of Aβ to accumulate iron, offering an explanation for previously observed local increases in iron concentration associated with AD lesions. Furthermore, the ability of iron to form redox-active iron phases from ferric precursors provides an origin both for the redox-active iron previously witnessed in AD tissue, and the increased levels of oxidative stress characteristic of AD. These interactions between Aβ and iron deliver valuable insights into the process of AD progression, which may ultimately provide targets for disease therapies
|
Mar 2014
|
|
I10-Beamline for Advanced Dichroism
|
Diamond Proposal Number(s):
[7670, 8731]
Open Access
Abstract: Recent work has demonstrated increased levels of redox-active iron biominerals in Alzheimer’s disease (AD) tissue. However, the origin, nature, and role of iron in AD pathology remains unclear. Using X-ray absorption, X-ray microspectroscopy, and electron microscopy techniques, we examined interactions between the AD peptide β-amyloid (Aβ) and ferrihydrite, which is the ferric form taken when iron is stored in humans. We report that Aβ is capable of reducing ferrihydrite to a pure iron(II) mineral
WHERE antiferromagnetically ordered Fe2+ cations occupy two nonequivalent crystal symmetry sites. Examination of these iron(II) phases following air exposure revealed a material consistent with the iron(II)-rich mineral magnetite. These results demonstrate the capability of Aβ to induce the redox-active biominerals reported in AD tissue from natural iron precursors. Such interactions between Aβ and ferrihydrite shed light upon the processes of AD pathogenesis, while providing potential targets for future therapies.
|
Feb 2014
|
|
I06-Nanoscience
I10-Beamline for Advanced Dichroism
|
S. E.
Harrison
,
L.
Collins-mcintyre
,
S.
Li
,
A.
Baker
,
L.
Shelford
,
Y.
Huo
,
A.
Pushp
,
S. S. P.
Parkin
,
J. S.
Harris
,
E.
Arenholz
,
G.
Van Der Laan
,
T.
Hesjedal
Abstract: Incorporation of magnetic dopants into topological insulators to break time-reversal symmetry is a prerequisite for observing the quantum anomalous Hall (QAHE) effect and other novel magnetoelectric phenomena. GdBiTe3 with a Gd:Bi ratio of 1:1 is a proposed QAHE system, however, the reported solubility limit for Gd doping into Bi2Te3 bulk crystals is between ?0.01 and 0.05. We present a magnetic study of molecular beam epitaxy grown (Gd x Bi1– x )2Te3 thin films with a high Gd concentration, up to x ? 0.3. Magnetometry reveals that the films are paramagnetic down to 1.5?K. X-ray magnetic circular dichroism at the Gd M 4,5 edge at 1.5?K reveals a saturation field of ?6?T, and a slow decay of the magnetic moment with temperature up to 200?K. The Gd3+ ions, which are substitutional on Bi sites in the Bi2Te3 lattice, exhibit a large atomic moment of ?7?? B , as determined by bulk-sensitive superconducting quantum interference device magnetometry. Surface oxidation and the formation of Gd2O3 lead to a reduced moment of ?4?? B as determined by surface-sensitive x-ray magnetic circular dichroism. Their large atomic moment makes these films suitable for incorporation into heterostructures, where interface polarization effects can lead to the formation of magnetic order within the topological insulators.
|
Jan 2014
|
|
I06-Nanoscience
|
M.
Marcham
,
L.
Shelford
,
S.
Cavill
,
P
Keatley
,
W.
Yu
,
P.
Shafer
,
A.
Neudert
,
J. R.
Childress
,
J. A.
Katine
,
E.
Arenholz
,
N.
Telling
,
G.
Van Der Laan
,
R.
Hicken
Abstract: Element-specific phase-resolved x-ray ferromagnetic resonance (FMR) was used to study spin pumping within Co50Fe50(3)/Cu(6)/Ni80Fe20(5) (thicknesses in nanometers) spin valve structures with large areas, so that edge effects typical of nanopillars used in standard magnetotransport experiments could be neglected. The phase of precession of the Co50Fe50 fixed layer was recorded as FMR was induced in the Ni80Fe20 free layer. The field ependence of the fixed layer phase contains a clear signature of spin transfer torque (STT) coupling due to spin pumping. Fitting the phase delay yields the spin-mixing conductance, the quantity that controls all spin transfer phenomena. The STT coupling is destroyed by insertion of Ta into the middle of the Cu layer.
|
May 2013
|
|
|
|
James
Byrne
,
Vicky
Coker
,
Sandhya
Moise
,
P. L.
Wincott
,
D. J.
Vaughan
,
Floriana
Tuna
,
Elke
Arenholz
,
Gerrit
Van Der Laan
,
Richard
Pattrick
,
Jon
Lloyd
,
Neil
Telling
Abstract: Cobalt-doped magnetite (CoxFe3-xO4) nanoparticles have been produced through the microbial reduction of cobalt-iron oxyhydroxide by the bacterium Geobacter sulfurreducens. The materials produced, as measured by superconducting quantum interference device magnetometry, X-ray magnetic circular dichroism, Mossbauer spectroscopy, etc., show dramatic increases in coercivity with increasing cobalt content without a major decrease in overall saturation magnetization. Structural and magnetization analyses reveal a reduction in particle size to less than 4 nm at the highest Co content, combined with an increase in the effective anisotropy of the magnetic nanoparticles. The potential use of these biogenic nanoparticles in aqueous suspensions for magnetic hyperthermia applications is demonstrated. Further analysis of the distribution of cations within the ferrite spinel indicates that the cobalt is predominantly incorporated in octahedral coordination, achieved by the substitution of Fe2+ site with Co2+, with up to 17 per cent Co substituted into tetrahedral sites.
|
Mar 2013
|
|
