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Open Access
Abstract: Conventional battery cathodes are limited by the redox capacity of the transition metal components. For example, the delithiation of LiCoO2 involves the formal oxidation from Co(III) to Co(IV). Enhanced capacities can be achieved if the anion also contributes to reversible oxidation. The origins of redox activity in crystals are difficult to quantify from experimental measurements or first-principles materials modelling. We present practical procedures to describe the electrostatic (Madelung potential) and electronic (integrated density of states) contributions, which are applied to the LiMO2 and Li2 MO3 (M = Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt, Au) model systems. We discuss how such descriptors could be integrated in a materials design workflow.
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Sep 2020
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I09-Surface and Interface Structural Analysis
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Leanne A. H.
Jones
,
Wojciech M.
Linhart
,
Nicole
Fleck
,
Jack E. N.
Swallow
,
Philip A. E.
Murgatroyd
,
Huw
Shiel
,
Thomas J.
Featherstone
,
Matthew J.
Smiles
,
Pardeep K.
Thakur
,
Tien-lin
Lee
,
Laurence J.
Hardwick
,
Jonathan
Alaria
,
Frank
Jaeckel
,
Robert
Kudrawiec
,
Lee A.
Burton
,
Aron
Walsh
,
Jonathan M.
Skelton
,
Tim D.
Veal
,
Vin R.
Dhanak
Diamond Proposal Number(s):
[21431]
Open Access
Abstract: The effects of Sn
5
s
lone pairs in the different phases of Sn sulphides are investigated with photoreflectance, hard x-ray photoemission spectroscopy (HAXPES), and density functional theory. Due to the photon energy-dependence of the photoionization cross sections, at high photon energy, the Sn
5
s
orbital photoemission has increased intensity relative to that from other orbitals. This enables the Sn
5
s
state contribution at the top of the valence band in the different Sn-sulphides, SnS,
Sn
2
S
3
, and
SnS
2
, to be clearly identified. SnS and
Sn
2
S
3
contain Sn(II) cations and the corresponding Sn
5
s
lone pairs are at the valence band maximum (VBM), leading to
∼
1.0
–1.3 eV band gaps and relatively high VBM on an absolute energy scale. In contrast,
SnS
2
only contains Sn(IV) cations, no filled lone pairs, and therefore has a
∼
2.3
eV room-temperature band gap and much lower VBM compared with SnS and
Sn
2
S
3
. The direct band gaps of these materials at 20 K are found using photoreflectance to be 1.36, 1.08, and 2.47 eV for SnS,
Sn
2
S
3
, and
SnS
2
, respectively, which further highlights the effect of having the lone-pair states at the VBM. As well as elucidating the role of the Sn
5
s
lone pairs in determining the band gaps and band alignments of the family of Sn-sulphide compounds, this also highlights how HAXPES is an ideal method for probing the lone-pair contribution to the density of states of the emerging class of materials with
n
s
2
configuration.
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Jul 2020
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E02-JEM ARM 300CF
I14-Hard X-ray Nanoprobe
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Tiarnan A. S.
Doherty
,
Andrew J.
Winchester
,
Stuart
Macpherson
,
Duncan N.
Johnstone
,
Vivek
Pareek
,
Elizabeth M.
Tennyson
,
Sofiia
Kosar
,
Felix U.
Kosasih
,
Miguel
Anaya
,
Mojtaba
Abdi-jalebi
,
Zahra
Andaji-garmaroudi
,
E. Laine
Wong
,
Julien
Madéo
,
Yu-hsien
Chiang
,
Ji-sang
Park
,
Young-kwang
Jung
,
Christopher E.
Petoukhoff
,
Giorgio
Divitini
,
Michael K. l.
Man
,
Caterina
Ducati
,
Aron
Walsh
,
Paul A.
Midgley
,
Keshav M.
Dani
,
Samuel D.
Stranks
Diamond Proposal Number(s):
[19023, 19793]
Abstract: Halide perovskite materials have promising performance characteristics for low-cost optoelectronic applications. Photovoltaic devices fabricated from perovskite absorbers have reached power conversion efficiencies above 25 per cent in single-junction devices and 28 per cent in tandem devices. This strong performance (albeit below the practical limits of about 30 per cent and 35 per cent, respectively) is surprising in thin films processed from solution at low-temperature, a method that generally produces abundant crystalline defects. Although point defects often induce only shallow electronic states in the perovskite bandgap that do not affect performance, perovskite devices still have many states deep within the bandgap that trap charge carriers and cause them to recombine non-radiatively. These deep trap states thus induce local variations in photoluminescence and limit the device performance. The origin and distribution of these trap states are unknown, but they have been associated with light-induced halide segregation in mixed-halide perovskite compositions and with local strain, both of which make devices less stable. Here we use photoemission electron microscopy to image the trap distribution in state-of-the-art halide perovskite films. Instead of a relatively uniform distribution within regions of poor photoluminescence efficiency, we observe discrete, nanoscale trap clusters. By correlating microscopy measurements with scanning electron analytical techniques, we find that these trap clusters appear at the interfaces between crystallographically and compositionally distinct entities. Finally, by generating time-resolved photoemission sequences of the photo-excited carrier trapping process, we reveal a hole-trapping character with the kinetics limited by diffusion of holes to the local trap clusters. Our approach shows that managing structure and composition on the nanoscale will be essential for optimal performance of halide perovskite devices.
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Apr 2020
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Abstract: Metal oxides can act as insulators, semiconductors, or metals depending on their chemical composition and crystal structure. Metal oxide semiconductors, which support equilibrium populations of electron and hole charge carriers, have widespread applications including batteries, solar cells, and display technologies. It is often difficult to predict in advance whether these materials will exhibit localized or delocalized charge carriers upon oxidation or reduction. We combine data from first-principles calculations of the electronic structure and dielectric response of 214 metal oxides to predict the energetic driving force for carrier localization and transport. We assess descriptors based on the carrier effective mass, static polaron binding energy, and Fröhlich electron–phonon coupling. Numerical analysis allows us to assign p- and n-type transport of a metal oxide to three classes: (i) band transport with high mobility; (ii) small polaron transport with low mobility; and (iii) intermediate behavior. The results of this classification agree with observations regarding carrier dynamics and lifetimes and are used to predict 10 candidate p-type oxides.
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Jan 2020
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Abstract: LiCoO2 is the prototypical cathode in lithium-ion batteries. Its crystal structure consists of Li+ and CoO2– layers that alternate along the hexagonal ⟨0001⟩ axis. It is well established that the ionic and electronic conduction are anisotropic, but little is known regarding the heat transport. We analyze the phonon dispersion and lifetimes using anharmonic lattice dynamics based on quantum-chemical force constants. Around room temperature, the thermal conductivity in the hexagonal ab plane of the layered cathode is ∼6 times higher than that along the c axis. An upper limit to the average thermal conductivity at T = 300 K of 38.5 W m–1 K–1 is set by short phonon lifetimes associated with anharmonic interactions within the octahedral face-sharing CoO2– network. Observations of conductivity <10 W m–1 K–1 can be understood by additional scattering channels including grain boundaries in polycrystalline samples. The impact on thermal processes in lithium-ion batteries is discussed.
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Sep 2019
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I09-Surface and Interface Structural Analysis
|
Daniel W.
Davies
,
Aron
Walsh
,
James J.
Mudd
,
Chris F.
Mcconville
,
Anna
Regoutz
,
J. Matthias
Kahk
,
David J.
Payne
,
Vin R.
Dhanak
,
David
Hesp
,
Katariina
Pussi
,
Tien-lin
Lee
,
Russell G.
Egdell
,
Kelvin H. L.
Zhang
Diamond Proposal Number(s):
[8441]
Abstract: Indium oxide is widely used as transparent electrode in optoelectronic devices and as a photocatalyst with activity for reduction of CO2. However, very little is known about the structural and electronic properties of its surfaces, particularly those prepared under reducing conditions. In this report, directional ‘lone-pair’ surface states associated with filled 5s2 orbitals have been identified on vacuum-annealed In2O3(111) through a combination of hard and soft X-ray photoemission spectroscopy and density functional theory calculations. The lone pairs reside on indium ad-atoms in a formal +1 oxidation state, each of which traps two electrons into a localised hybrid orbital protruding away from the surface and lying just above the valence band maximum in photoemission spectra. The third electron associated with the ad-atoms is delocalised into the conduction band, thus producing the surface electron accumulation layer identified previously on vacuum-annealed In2O3(111) (1×1) surfaces. The surface structure is further supported by low energy electron diffraction, but there is no chemical shift in indium core level x-ray photoelectron spectra between surface In(I) ad-atoms and bulk In(III). The 5s2 lone pairs confer Lewis basicity on the surface In sites and may have a pronounced impact on the catalytic or photo-catalytic activity of reduced In2O3.
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Dec 2018
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Abstract: The concepts of oxidation state and atomic charge are entangled in modern materials science. We distinguish between these quantities and consider their fundamental limitations and utility for understanding material properties. We discuss the nature of bonding between atoms and the techniques that have been developed for partitioning electron density. While formal oxidation states help us count electrons (in ions, bonds, lone pairs), variously defined atomic charges are usefully employed in the description of physical processes including dielectric response and electronic spectroscopies. Such partial charges are introduced as quantitative measures in simple mechanistic models of a more complex reality, and therefore may not be comparable or transferable. In contrast, oxidation states are defined to be universal, with deviations constituting exciting challenges as evidenced in mixed-valence compounds, electrides and highly correlated systems. This Perspective covers how these concepts have evolved in recent years, our current understanding and their significance.
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Oct 2018
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I19-Small Molecule Single Crystal Diffraction
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Diamond Proposal Number(s):
[17379]
Abstract: “Breathing” metal-organic frameworks (MOFs) exhibiting changes in their structural and physical properties upon an external stimulus are an interesting class of crystalline materials due to their potential applications including chemical sensors. The addition of redox activity opens up a new pathway for multi-functional “breathing” frameworks. Herein we report the continuous breathing behavior of a tetrathiafulvalene (TTF)-based MOF showing a reversible swelling (up to ca. 40% of the volume cell) upon solvent adsorption. Importantly, the planarity of the TTF linkers is influenced by the breathing behavior, directly impacting on their electrochemical properties, thus opening the way for the development of new electrochemical sensors. Quantum chemical calculations and Raman spectroscopy have been used to provide insights into the tunability of the oxidation potential.
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Jul 2018
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Theoretical Physics
|
Abstract: The source of n-type conductivity in undoped transparent conducting oxides has been a topic of debate for several decades. The point defect of most interest in this respect is the oxygen vacancy, but there are many conflicting reports on the shallow versus deep nature of its related electronic states. Here, using a hybrid quantum mechanical/molecular mechanical embedded cluster approach, we have computed formation and ionization energies of oxygen vacancies in three representative transparent conducting oxides: In2O3,SnO2, and ZnO. We find that, in all three systems, oxygen vacancies form well-localized, compact donors. We demonstrate, however, that such compactness does not preclude the possibility of these states being shallow in nature, by considering the energetic balance between the vacancy binding electrons that are in localized orbitals or in effective-mass-like diffuse orbitals. Our results show that, thermodynamically, oxygen vacancies in bulk In2O3 introduce states above the conduction band minimum that contribute significantly to the observed conductivity properties of undoped samples. For ZnO and SnO2, the states are deep, and our calculated ionization energies agree well with thermochemical and optical experiments. Our computed equilibrium defect and carrier concentrations, however, demonstrate that these deep states may nevertheless lead to significant intrinsic n-type conductivity under reducing conditions at elevated temperatures. Our study indicates the importance of oxygen vacancies in relation to intrinsic carrier concentrations not only in In2O3, but also in SnO2 and ZnO.
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May 2018
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I24-Microfocus Macromolecular Crystallography
|
M. J.
Bryant
,
J. M.
Skelton
,
L. E.
Hatcher
,
C.
Stubbs
,
E.
Madrid
,
A. R.
Pallipurath
,
L. H.
Thomas
,
Ch. H.
Woodall
,
J.
Christensen
,
S.
Fuertes
,
T. P.
Robinson
,
C. M.
Beavers
,
S. J.
Teat
,
M.
Warren
,
F.
Pradaux-caggiano
,
A.
Walsh
,
F.
Marken
,
D. R.
Carbery
,
S. C.
Parker
,
N. B.
Mckeown
,
R.
Malpass-evans
,
M.
Carta
,
P. R.
Raithby
Open Access
Abstract: Selective, robust and cost-effective chemical sensors for detecting small volatile-organic compounds (VOCs) have widespread applications in industry, healthcare and environmental monitoring. Here we design a Pt(II) pincer-type material with selective absorptive and emissive responses to methanol and water. The yellow anhydrous form converts reversibly on a subsecond timescale to a red hydrate in the presence of parts-per-thousand levels of atmospheric water vapour. Exposure to methanol induces a similarly-rapid and reversible colour change to a blue methanol solvate. Stable smart coatings on glass demonstrate robust switching over 104 cycles, and flexible microporous polymer membranes incorporating microcrystals of the complex show identical vapochromic behaviour. The rapid vapochromic response can be rationalised from the crystal structure, and in combination with quantum-chemical modelling, we provide a complete microscopic picture of the switching mechanism. We discuss how this multiscale design approach can be used to obtain new compounds with tailored VOC selectivity and spectral responses.
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Dec 2017
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