I11-High Resolution Powder Diffraction
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Alexandra
Morscher
,
Lucia
Corti
,
Samuel L.
Goodwin
,
Andres
Acin-Lalanza
,
Matthew
Wright
,
T. Wesley
Surta
,
Ruiyong
Chen
,
Matthew S.
Dyer
,
Frédéric
Blanc
,
Luke M.
Daniels
,
John B.
Claridge
,
Matthew J.
Rosseinsky
Diamond Proposal Number(s):
[37989]
Open Access
Abstract: Sulfide lithium argyrodites are a key materials family that are studied as solid electrolytes in commercial all-solid-state batteries (ASSBs), while their oxide analogues remain relatively unexplored. This study presents the discovery of Li7TiO5X (X = Cl–, Br–), the first lithium argyrodite materials in which a transition metal is used as the framework-forming cation, expanding the chemical space that is accessible for oxide argyrodites. Incorporation of Ti4+ enables the lithium content to be maximized to 7 Li+ per formula unit. Interestingly, even with the high lithium content, Li7TiO5Cl retains a Li+ site disordered cubic F4̅3m structure at room temperature with Li+ occupancy of the T5, T5a, and T3 positions, and exhibits an ionic conductivity of 2.2(2) × 10–6 S cm–1 with the lowest reported activation energy (0.36(2) eV) for bulk Li+ ion transport in an oxide argyrodite. Conversely, Li7TiO5Br adopts the same F4̅3m symmetry at room temperature but with an ordered arrangement of Li+ positions via full occupancy of the T5a and T3 positions, and thus has an ionic conductivity that is 3 orders of magnitude lower (∼10–9 S cm–1) and a much higher activation energy (0.58(2) eV) than Li7TiO5Cl. Order–disorder behavior is observed below 250 K in Li7TiO5Cl, where a Li+ site ordering pattern is observed that is distinct from Li7TiO5Br and all sulfide argyrodites, yielding a tetragonal symmetry (I4̅) for only the second time to date in the argyrodite structure type. This unique order–disorder behavior, alongside the ability to incorporate transition metal cations within this material family emphasizes the potential to access much greater structural diversity via the expansive chemical space that is available for exploration in oxide argyrodites.
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Jun 2026
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I11-High Resolution Powder Diffraction
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Brinda
Kuthanazhi
,
Debalina
Banerjee
,
Dmitry
Maslennikov
,
Andrij
Vasylenko
,
Jan P.
Scheifers
,
Cara J.
Hawkins
,
Daniel
Ritchie
,
Craig M.
Robertson
,
Marco
Zanella
,
Troy D.
Manning
,
Luke M.
Daniels
,
Marina R.
Filip
,
Matthew S.
Dyer
,
Laura M.
Herz
,
John B.
Claridge
,
Matthew J.
Rosseinsky
Diamond Proposal Number(s):
[37989]
Open Access
Abstract: We explore multiple-cation chalco–halide phase fields evaluated by their synthetic accessibility using machine learning models. Exploratory synthesis guided by computational tools leads to the discovery of two new compounds; CuSn2SI3 and Cu0.35Sn5.29S2I7, their structures, and electronic and optical properties are reported herein. This is the first report of a stable quaternary compound in the Cu–Sn–S–I phase field. The two new compounds show related crystal structures where Sn4S2I4 layers are a common structural motif in both. These Sn4S2I4 layers are connected by Cu2I2 layers and disordered Cu–Sn–I layers, forming the three-dimensional structures of CuSn2SI3 and Cu0.35Sn5.29S2I7 respectively. Electronic band structure calculations using density functional theory show the presence of a direct band gap in CuSn2SI3 and suggest anisotropic transport, in line with the layered structure of the compound. A mixture of the two compounds with ∼86% CuSn2SI3, shows a band gap in the visible region, close to 2.1 eV and a significant photo-induced charge carrier mobility of ∼1.3 cm2 V−1 s−1. This demonstrates Cu–Sn chalco–halides can form a promising phase space to explore for solar absorber materials, with further design and tuning of band gap.
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Mar 2026
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I11-High Resolution Powder Diffraction
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Open Access
Abstract: The first reported phase in the Y2O3–NiO–TiO2 chemical space, the Y2NiTiO6 perovskite undergoes a temperature-induced order–disorder transition. Above ∼1700 K, it adopts the structure of a disordered CaTiO3-type orthorhombic perovskite with a = 5.26939(2), b = 5.60367(2), and c = 7.58137(3) Å, with the B site uniformly occupied by 0.5Ni+0.5Ti. Below this temperature, Y2NiTiO6 adopts rock-salt ordering of the transition metals in a monoclinic unit cell (a = 5.26695(2), b = 5.60164(2), c = 7.57493(2) Å, β = 90.4940(2)°) with 0.9/0.1 ordering of the B site. Ordering of Ni and Ti changes the magnetic properties from spin-glass behavior in the orthorhombic phase to antiferromagnetic order (TN = 17 K) for the monoclinic phase, while the optical properties of both phases remain unchanged across the transition.
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Oct 2025
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I11-High Resolution Powder Diffraction
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Jungwoo
Lim
,
Manel
Sonni
,
Luke M.
Daniels
,
Mounib
Bahri
,
Marco
Zanella
,
Ruiyong
Chen
,
Zhao
Li
,
Alex R.
Neale
,
Hongjun
Niu
,
Nigel D.
Browning
,
Matthew S.
Dyer
,
John B.
Claridge
,
Laurence J.
Hardwick
,
Matthew J.
Rosseinsky
Diamond Proposal Number(s):
[31578]
Open Access
Abstract: LiNiO2 positive electrode materials for lithium-ion batteries have experienced a revival of interest due to increasing technological energy demands. Herein a specific Ti4+ substitution is targeted into LiNiO2 to access new compositions by synthesizing the LiNi1–xTi3x/4O2 solid solution with the aim of retaining Ni3+. Compositions in the range 0.025 ≤ x ≤ 0.2 form nanocomposites of compositionally homogeneous ordered R
m and disordered Fm
m rock salt domains as observed via X-ray and neutron diffraction, and STEM. The disordered rock salt domains stabilize the ordered structure to provide excellent structural reversibility via the formation of coherent interfaces during cycling and enable deep delithiation using a constant voltage charging step without structural degradation. The detrimental structural phase transitions associated with the poor cyclability of LiNiO2 are suppressed to yield a low strain positive electrode material with high capacity retention that offers high-rate capability even under increased cell electrode mass loadings. The composition x = 0.075 (LiNi0.925Ti0.05625O2) affords a 93% capacity retention after 100 cycles (100 mA g−1) and demonstrates high reversible capacities of 125 mAh g−1 even under rates of 3200 mA g−1. LiNi0.925Ti0.05625O2 exhibits exceptional performance at electrode mass loadings (13.6 mg cm−2) comparable to those required for commercial cell applications.
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Jul 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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I11-High Resolution Powder Diffraction
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Matthew J.
Rosseinsky
,
Moinak
Dutta
,
Angelos B.
Canaj
,
Tilen
Knaflič
,
Christopher M.
Collins
,
Troy D.
Manning
,
Hongjun
Niu
,
Luke M.
Daniels
,
Aikaterini
Vriza
,
Luke A.
Johnson
,
Bhupendra
Mali
,
Yuri
Tanuma
,
Todd Wesley
Surta
,
John B.
Claridge
,
Neil
Berry
,
Denis
Arčon
,
Matthew S.
Dyer
Open Access
Abstract: We report the synthesis, structural characterization and magnetic properties of K3coronene, and demonstrate a computational screening workflow designed to accelerate the discovery of metal intercalated polycyclic aromatic hydrocarbon (PAH), a class of materials of interest following reports of superconductivity, but lacking demonstrated and understood characterised materials compositions. Coronene is identified as a suitable PAH candidate from a library of PAHs for potassium intercalation by computational screening of their electronic structure and of the void space in their crystal structures, targeting LUMO similarity to C60 and the availability of suitable sites to accommodate inserted cations. Convex hull calculations with energies from crystal structure prediction based on ion insertion into the identified void space of coronene suggest that the x = 3 composition in Kxcoronene is stable at 0 K, reinforcing the suitability of coronone for experimental investigation. Exploration of reaction conditions and compositions revealed that the mild reducing agent KH allows formation of K3coronene. The structure of K3coronene solved from synchrotron powder X-ray diffraction features extensive reorientation and associated disorder of coronene molecules compared with the parent pristine host. This is driven by K+ intercalation and occupation of sites both within and between the coronene stacks that are partially retained from the parent structure. This disruption of the host structure is greater when three cations are inserted per coronene than in reported metal PAH structures where the maximum ratio of cations to PAH is 2. Superconductivity is not observed, contrary to previous reports on Kxcoronene. The expected localised moment response of coronene3- is suppressed, which may be associated with the combination of extensive disorder and close coronene3- - coronene3- contacts.
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Dec 2024
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I11-High Resolution Powder Diffraction
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Nataliya
Hulai
,
Marco
Zanella
,
Craig
Robertson
,
Daniel
Ritchie
,
Manel
Sonni
,
Matthew A.
Wright
,
Jon A.
Newnham
,
Cara J.
Hawkins
,
Jayne
Whitworth
,
Bhupendra
Mali
,
Hongjun
Niu
,
Matthew S.
Dyer
,
Christopher M.
Collins
,
Luke M.
Daniels
,
John B.
Claridge
,
Matthew J.
Rosseinsky
Diamond Proposal Number(s):
[31578]
Open Access
Abstract: Two compounds were discovered in the well-studied BaO-Y2O3-SiO2 phase field. Two different experimental routines were used for the exploration of this system due to the differences of synthetic conditions and competition with a glass field. The first phase Ba5Y13[SiO4]8O8.5 was isolated through a combination of energy dispersive X-ray spectroscopy analysis and diffraction techniques which guided the exploration. The second phase Ba3Y2[Si2O7]2 was located using iterative algorithmic identification of target compositions. The structure solution of the new compounds was aided by continuous rotation electron diffraction, and the structures were refined against combined synchrotron and neutron time-of-flight powder diffraction. Ba5Y13[SiO4]8O8.5 crystallizes in I-42m, a = 18.92732(1), c = 5.357307(6) Å and represents its own structure type which combines elements of structures of known silicates embedded in columns of interconnected yttrium-centred polyhedra characteristic of high-pressure phases. Ba3Y2[Si2O7]2 has P21 symmetry with a pseudo-tetragonal cell (a = 16.47640(4), b = 9.04150(5), c = 9.04114(7) Å, β = 90.0122(9)°) and is a direct superstructure of the Ca3BaBi[P2O7]2 structure. Despite the lower symmetry, the structure of Ba3Y2[Si2O7]2 retains disorder in both Ba/Y sites and disilicate network, thus presenting a superposition of possible locally-ordered fragments. Ba5Y13[SiO4]8O8.5 has low thermal conductivity of 1.04(5) W m-1 K-1 at room temperature. The two discovered phases provide a rich structural platform for further functional material design. The interplay of automated unknown phase composition identification with multiple diffraction methods offers acceleration of the time-consuming exploration of high-dimensional chemical spaces for new structures.
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Sep 2024
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I11-High Resolution Powder Diffraction
I19-Small Molecule Single Crystal Diffraction
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Datta
Markad
,
Laurence J.
Kershaw Cook
,
Rémi
Pétuya
,
Yong
Yan
,
Oliver
Gilford
,
Ajay
Verma
,
Bhupendra
Mali
,
Craig M.
Robertson
,
Neil G.
Berry
,
George R.
Darling
,
Matthew S.
Dyer
,
Dmytro
Antypov
,
Alexandros P.
Katsoulidis
,
Matthew J.
Rosseinsky
Diamond Proposal Number(s):
[31578, 36629]
Open Access
Abstract: Porous materials perform molecular sorting, separation and transformation by interaction between their framework structures and the substrates. Proteins also interact with molecules to effect chemical transformations, but rely on the precise sequence of the amino acid building units along a common polypeptide backbone to maximise their performance. Design strategies that positionally order sidechains over a defined porous framework to diversify the internal surface chemistry would enhance control of substrate processing. Here we show that different sidechains can be ordered over a metal-organic framework through recognition of their distinct chemistries during synthesis. The sidechains are recognised because each one forces the common building unit that defines the backbone of the framework into a different conformation in order to form the extended structure. The resulting sidechain ordering affords hexane isomer separation performance superior to that of the same framework decorated only with sidechains of a single kind. The separated molecules adopt distinct arrangements within the resulting modified pore geometry, reflecting their strongly differentiated environments precisely created by the ordered sidechains. The development of frameworks that recognise and order multiple sidechain functionality by conformational control offers tailoring of the internal surfaces within families of porous materials to direct interactions at the molecular level.
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Aug 2024
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I11-High Resolution Powder Diffraction
I19-Small Molecule Single Crystal Diffraction
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Guopeng
Han
,
Luke M.
Daniels
,
Andrij
Vasylenko
,
Kate A.
Morrison
,
Lucia
Corti
,
Chris M.
Collins
,
Hongjun
Niu
,
Ruiyong
Chen
,
Craig M.
Robertson
,
Frédéric
Blanc
,
Matthew S.
Dyer
,
John B.
Claridge
,
Matthew J.
Rosseinsky
Diamond Proposal Number(s):
[31578, 36629]
Open Access
Abstract: Ge4+ substitution into the recently discovered superionic conductor Li7Si2S7I is demonstrated by synthesis of Li7Si2–xGexS7I, where x ≤ 1.2. The anion packing and tetrahedral silicon location of Li7Si2S7I are retained upon substitution. Single crystal X-ray diffraction shows that substitution of larger Ge4+ for Si4+ expands the unit cell volume and further increases Li+ site disorder, such that Li7Si0.88Ge1.12S7I has one Li+ site more (sixteen in total) than Li7Si2S7I. The ionic conductivity of Li7Si0.8Ge1.2S7I (x = 1.2) at 303 K is 1.02(3) × 10–2 S cm–1 with low activation energies for Li+ transport demonstrated over a wide temperature range by AC impedance and 7Li NMR spectroscopy. All sixteen Li+ sites remain occupied to temperatures as low as 30 K in Li7Si0.88Ge1.12S7I as a result of the structural expansion. This differs from Li7Si2S7I, where the partial Li+ site ordering observed below room temperature reduces the ionic conductivity. The suppression of Li+ site depopulation by Ge4+ substitution retains the high mobility to temperatures as low as 200 K, yielding low temperature performance comparable with state-of-the-art Li ion conducting materials.
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Jun 2024
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I19-Small Molecule Single Crystal Diffraction
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Cara J.
Hawkins
,
Jon A.
Newnham
,
Batoul
Almoussawi
,
Nataliya L.
Gulay
,
Samuel L.
Goodwin
,
Marco
Zanella
,
Troy D.
Manning
,
Luke M.
Daniels
,
Matthew S.
Dyer
,
Tim D.
Veal
,
John B.
Claridge
,
Matthew J.
Rosseinsky
Diamond Proposal Number(s):
[30461]
Open Access
Abstract: Mixed anion halide-chalcogenide materials have recently attracted attention for a variety of applications, owing to their desirable optoelectronic properties. We report the synthesis of a previously unreported mixed-metal chalcohalide material, CuBiSeCl2 (Pnma), accessed through a simple, low-temperature solid-state route. The physical structure is characterized through single-crystal X-ray diffraction and reveals significant Cu displacement within the CuSe2Cl4 octahedra. The electronic structure of CuBiSeCl2 is investigated computationally, which indicates highly anisotropic charge carrier effective masses, and by experimental verification using X-ray photoelectron spectroscopy, which reveals a valence band dominated by Cu orbitals. The band gap is measured to be 1.33(2) eV, a suitable value for solar absorption applications. The electronic and thermal properties, including resistivity, Seebeck coefficient, thermal conductivity, and heat capacity, are also measured, and it is found that CuBiSeCl2 exhibits a low room temperature thermal conductivity of 0.27(4) W K–1 m–1, realized through modifications to the phonon landscape through increased bonding anisotropy.
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Apr 2024
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