I09-Surface and Interface Structural Analysis
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Bhavya
Rakheja
,
Adam
Hultqvist
,
Rahul Mahavir
Varma
,
Natalia M.
Martin
,
Karen
Radetzky
,
Stefania
Riva
,
Evelyn
Johannesson
,
Ute B.
Cappel
,
Hakan
Rensmo
,
Erik M. J.
Johansson
,
Tobias
Torndahl
Diamond Proposal Number(s):
[35209]
Open Access
Abstract: Tin oxide (SnOx) by atomic-layer deposition (ALD), in combination with fullerene, is widely employed as an electron transport layer in p–i–n perovskite solar cells. This study investigates the direct deposition of ALD SnOx on top of formamidinium (FA)-based perovskites, as a step toward the elimination of the fullerene interlayer and its poor effect on solar cell’s long-term stability. The interfacial chemistry between FA-based perovskites (FAPbI3 and FAPbBr3) and ALD SnOx was studied using soft and hard X-ray photoelectron spectroscopy (SOXPES and HAXPES) with a focus on investigating the separate roles FA and different halides play during interface formation. FAPbI3 and FAPbBr3 solar cell structures solely containing ALD SnOx resulted in s-shaped current–voltage characteristics, indicating the formation of a transport barrier at the interface. Both SOXPES and HAXPES measurements revealed the emergence of additional nitrogen states at the interface during the ALD SnOx deposition on FAPbI3 and FAPbBr3, where these states are linked to the decomposition of FA+. The FAPbI3/ALD SnOx interface also showed the presence of lead iodide (PbI2) through additional lead states other than that from FAPbI3 by using SOXPES measurements. Concerning the FAPbBr3/ALD SnOx interface, no additional lead states were observed; however, measurements instead revealed the formation of Sn–Br bonds at the interface along with the migration of bromine ions into the bulk of the ALD SnOx. Thus, FAPbI3 and FAPbBr3 undergo distinct reaction pathways upon direct deposition of ALD SnOx on top of them. We reason that the decomposition of FA+ in both perovskites and the formation of PbI2 at the FAPbI3/ALD SnOx interface and the incorporation of Br in SnOx at the FAPbBr3/ALD SnOx interface prove detrimental toward device performance. Therefore, careful interfacial engineering that can mitigate the formation of these products should be utilized to enhance the performance of perovskite solar cells.
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Jun 2025
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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
I11-High Resolution Powder Diffraction
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Tao
Zeng
,
Ziqin
Jiao
,
Xiaoyu
Gao
,
Maolin
Yang
,
Xiaohu
Wang
,
Wenguang
Zhao
,
Wei
Tang
,
Mihai
Chu
,
Ze
He
,
Jinqi
Li
,
Zhongyuan
Huang
,
Guojie
Chen
,
Ziwei
Chen
,
Rui
Wang
,
Liming
Wang
,
Junrong
Zhang
,
Lunhua
He
,
Yuguang
Pu
,
Yinguo
Xiao
Diamond Proposal Number(s):
[36187, 34243]
Abstract: Li-rich manganese-based oxides (LRMO) are promising cathode materials for next-generation lithium-ion batteries due to their high-capacity and low-cost merits. However, the low initial coulombic efficiency (ICE) and irreversible oxygen release of LRMO severely hinder their commercialization processes. Here, we employ glyoxal treatment to modulate the hybridization between transition metal (TM) 3d and oxygen (O) 2p orbitals in LRMO. This approach is found to reduce the Co/Mn t2g-O 2p hybridization in LRMO while simultaneously activating the Co2+/Co3+ redox below the Fermi level. Our findings demonstrate that tuning TM 3d-O 2p orbital hybridization can be a viable approach to improve the ICE of LMRO. Specifically, the ICE of LRMO can be elevated from 85.3 % to 102.5 %, and a high specific capacity of 291.2 mAh g−1 can be achieved at 0.1 C. Moreover, the treated LRMO cathodes exhibit significantly enhanced capacity retention.
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May 2025
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I16-Materials and Magnetism
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Ludmila
Leroy
,
Shih-Wen
Huang
,
Chun-Chien
Chiu
,
Sheng-Zhu
Ho
,
Janine
Dössegger
,
Cinthia
Piamonteze
,
Yi-Chun
Chen
,
Elsa
Abreu
,
Alessandro
Bombardi
,
Jan-Chi
Yang
,
Urs
Staub
Open Access
Abstract: Thin films’ properties can be greatly influenced by their supporting growth substrates. Even in the so-called strain-free heterostructure films, it is still unclear whether there will be no interfacial electronic reconstructions induced by the underlying substrates. Here, we report the studies of SrTiO3 (STO) films in the freestanding form (FS) with a thickness ranging from 20 to 80 nm. These STO films, by default, are in a strain-free state; they exhibit distinct properties not seen in both bulk and strain-free heterostructure forms. Our films show an enhanced antiferrodistortive (AFD) phase transition temperature with a preferential in-plane rotation axis for the TiO6 octahedra. The anisotropic Ti orbital occupancy around the surface signals the departure of its properties from the bulk. Moreover, we have found that the in-plane ferroelectricity can be strengthened by the reduced dimensionality, establishing that the dimensionality control is an important factor for enhancing STO’s ferroelectric response.
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May 2025
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I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[28349]
Open Access
Abstract: An understanding of the nature of the grain boundaries and impurity phases contained in complex mixed metal oxide solid electrolytes is key to the development of improved and more stable solid-state batteries with reduced grain boundary resistances and higher ionic conductivities of the bulk sample. The Li-ion solid electrolyte Li7La3Zr2O12 (LLZO) is one of the most researched electrolytes in the field due to its high ionic conductivity, thermal stability, and wide voltage stability window. Despite its potential, the nature of the impurity and surface phases formed during the synthesis of LLZO and their role and influence on LLZO’s performance when used as an electrolyte remain poorly understood and controlled. In addition, there are limited characterization methods available for detailed studies of these impurity phases, particularly if these phases are buried in or close to the grain boundaries of a dense sintered material. Here, we demonstrate a solid-state nuclear magnetic resonance (ssNMR) and dynamic nuclear polarization (DNP) approach that exploits both endogenous and exogenous dopants to select for either specific impurities or separate bulk vs surface/subsurface phases. Specifically, the location of Al-containing phases within an Al doped LLZO and the impurity phases that form during synthesis are mapped: by doping LLZO with trace amounts of paramagnetic metal ions (Fe3+ and Gd3+), DNP is used to selectively probe Al- and La-containing impurity phases, respectively, allowing us to enhance the signals arising from the LiAlO2 and LaAlO3 impurities and to confirm their identity. A 17O DNP experiment using Gd3+ doped LLZO is performed to identify further La3+-containing impurities (specifically La2Zr2O7 and La2O3). Finally, a 7Li DNP irradiated 7Li–27Al dipolar-based heteronuclear multiple quantum correlation experiment is performed by using the radical TEKPol as the polarization agent. This experiment demonstrates that the poorly crystalline LiAlO2 that is found close to the surfaces of the LLZO composite is coated by a thin Li-containing impurity layer and thus not directly present at the surface.
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May 2025
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B18-Core EXAFS
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Diamond Proposal Number(s):
[31218]
Open Access
Abstract: Several classes of inorganic transparent conducting coatings are available (broad band wide band gap semiconductors, noble metals, amorphous oxides and correlated metals), with peak performance depending on the layer thickness. Correlated metallic transition metal oxides have emerged as potential competitive materials for small coating thicknesses, but their peak performance remains one order of magnitude below other best in class materials. By exploiting the charge transfer at the interface between a correlated metal (SrNbO3) and a wide band gap semiconductor (SrTiO3), we show that pulsed laser deposition-grown SrNbO3 heterostructures on SrTiO3 outperform correlated metals by an order of magnitude. The apparent increase in carrier concentration confirms that an electronically active interfacial layer is contributing to the transport properties of the heterostructure. The correlated metallic electrode allows the extraction of high mobility carriers resulting in an enhanced conductivity for heterostructures with thicknesses up to 20 nm. The high optical absorption of the high mobility metallic interface does not have a detrimental effect on the transmission of the heterostructure due to its small thickness. The charge transfer-driven enhanced electrical properties in correlated metal - wide band gap semiconductor heterostructures offer a distinct route to high performance transparent conducting materials.
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May 2025
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I09-Surface and Interface Structural Analysis
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Open Access
Abstract: The three-dimensional recording scheme of time-of-flight momentum microscopes (ToF-MMs) is advantageous for fast mapping of the photoelectron distribution in (E,k) parameter space over the entire Brillouin zone. However, the 2 ns pulse period of most synchrotrons is too short for pure ToF photoelectron spectroscopy. The use of a hemispherical analyzer (HSA) as a pre-filter allows ToF-MM at such high pulse rates. The first HSA & ToF hybrid MM is operated at the soft X-ray branch of beamline I09 at the Diamond Light Source, UK. The photon energy ranges from 105 eV to 2 keV, with circular polarization available for hν ≥ 145 eV. The HSA reduces the transmitted energy band to typically 0.5 eV, which is then further analyzed by ToF recording. In initial experiments, the overall efficiency gain when switching from the standard 2D (kx,ky) mode to the 3D (kx,ky,Ekin) hybrid mode was about 24. This value is determined by the number of resolved kinetic energies (here 12) and the transmission gain of the electron optics due to the high pass energy of the HSA in hybrid mode (Epass up to 500 eV). The transmission gain depends on the size of the photon footprint on the sample. Under k-imaging conditions, the energy and momentum resolution are 10.2 meV (FWHM) (4.2 meV with 200 μm slits and Epass = 8 eV) and 0.010 Å-1. The energy filtered X-PEEM mode showed a spatial resolution of 250 nm. As examples, we show 2D band mapping of bilayer graphene, 3D mapping of the Fermi surface of Cu, circular dichroic ARPES for intercalated indenene layers, and the sp valence band of Au. Full-field photoelectron diffraction patterns of Ge show rich structure in k-field diameters of up to 6 Å-1.
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May 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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I09-Surface and Interface Structural Analysis
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Qianhui
Liu
,
Tove
Ericson
,
Robert
Temperton
,
Ida
Kallquist
,
Fredrik
Lindgren
,
Laura
King
,
Alenka
Križan
,
Katie L.
Browning
,
Ethan
Crumlin
,
Gabriel M.
Veith
,
Maria
Hahlin
Diamond Proposal Number(s):
[36581]
Open Access
Abstract: The real-time interface chemistry between the lithium cobalt oxide (LCO) working electrode and the LiClO4/propylene carbonate (PC) electrolyte is investigated during lithiation/delithiation using dip-and-pull ambient pressure photoelectron spectroscopy (APXPS). The APXPS results appear to exhibit the seldom discussed Co2+ state in the LCO structure, where the operando measurements indicate electron transfer among Co2+, Co3+, and Co4+ states. Specifically, the lithiation of LCO reduces the Co4+ state to both Co3+ and Co2+ states, where, as a function of voltage, reduction to Co2+ state is initially more pronounced followed by Co3+ formation. In addition, a delay in surface delithiation is observed during the reverse potential steps. This is discussed in terms of overpotential at the interface measurement position as a consequence of the dip-and-pull setup for this experiment. Finally, the shifts in the apparent binding energies of the spectral features corresponding to the electrolyte and LCO at their interface shows that the electrochemical potentials at delithiation voltage steps are different from the lithiation steps at the same applied voltages. This further explains the non-responsive delithiation. The BE shift observed from the LCO surface is argued to be dominantly due to the semi-conductive nature of the sample. Overall, this article shows the importance of operando APXPS for probing non-equilibrium states in battery electrodes for understanding electron transfer in the reactions.
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May 2025
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I09-Surface and Interface Structural Analysis
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Francesco
Offi
,
Francesco
Borgatti
,
Pasquale
Orgiani
,
Vincent
Polewczyk
,
Sandeep Kumar
Chaluvadi
,
Shyni
Punathum Chalil
,
Aleksandr
Petrov
,
Federico
Motti
,
Gian Marco
Pierantozzi
,
Giancarlo
Panaccione
,
Bogdan
Rutkowski
,
Paolo
Mengucci
,
Gianni
Barucca
,
Deepnarayan
Biswas
,
Tien-Lin
Lee
,
Emiliano
Marchetti
,
Alberto
Martinelli
,
Davide
Peddis
,
Gaspare
Varvaro
Diamond Proposal Number(s):
[32921]
Open Access
Abstract: Epitaxial heterostructures integrating thin Fe3O4 films hold great potential for spintronics, magnetoionics, and multifunctional device development. In this work, the morpho-structural and magnetic properties of all-spinel Fe3O4/MgCr2O4/Fe3O4 trilayers grown on a MgCr2O4 buffer-layer, exhibiting very close lattice matching, were investigated by using both surface and bulk sensitive techniques. The close lattice match between Fe3O4 and MgCr2O4 enables the growth of epitaxial heterostructures with magnetically decoupled Fe3O4 layers for spacer thicknesses ≥ 1.6 nm, while reducing the formation of antiphase boundaries. Despite localized interphase diffusion, which leads to the formation of a mixed Cr/Fe spinel oxide with magnetically polarized Cr ions at the Fe3O4/MgCr2O4 interfaces, the overall magnetic properties remain largely consistent with those of the individual Fe3O4 layers. This study sheds light on the magnetic interactions within Fe3O4 layers mediated by a MgCr2O4 spacer, and demonstrates the feasibility of the approach in preserving the properties of thin Fe3O4 films, in complex heterostructures, thus offering a promising pathway for designing advanced all-spinel oxide devices.
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May 2025
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