I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[17193]
Open Access
Abstract: By tuning the A site cation size it is possible to control the degree of octahedral distortion and ultimately structural symmetry in the new perovskite solid solution La0.5Na0.5−xKxTiO3, affording a rhombohedral-to-cubic transition as x increases above 0.4. The La3+ and K+ cations are distributed randomly across the A site leading to significant phonon disorder in cubic La0.5K0.5TiO3 (Pm[3 with combining macron]m) which produces a phonon-glass with a thermal conductivity of 2.37(12) W m−1 K−1 at 300 K; a reduction of 75% when compared with isostructural SrTiO3. This simple cation substitution of Sr2+ for La3+ and K+ maintains the flexible structural chemistry of the perovskite structure and two mechanisms of doping for the introduction of electronic charge carriers are explored; A site doping in La1−yKyTiO3 or B site doping in La0.5K0.5Ti1−zNbzO3. The phonon-glass thermal conductivity of La0.5K0.5TiO3 is retained upon doping through both of these mechanisms highlighting how the usually strongly coupled thermal and electronic transport can be minimised by mass disorder in perovskites. Precise control over octahedral distortion in A site doped La1−yKyTiO3, which has rhombohedral (R[3 with combining macron]c) symmetry affords lower band dispersions and increased carrier effective masses over those achieved in B site doped La0.5K0.5Ti1−zNbzO3 which maintains the cubic (Pm[3 with combining macron]m) symmetry of the undoped La0.5K0.5TiO3 parent. The higher Seebeck coefficients of A site doped La1−yKyTiO3 yield larger power factors and lead to increased thermoelectric figures of merit and improved conversion efficiencies compared with the mechanism for B site doping.
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Jul 2018
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I11-High Resolution Powder Diffraction
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Abstract: The discovery of new materials is hampered by the lack of efficient approaches to the exploration of both the large number of possible elemental compositions for such materials, and of the candidate structures at each composition1. For example, the discovery of inorganic extended solid structures has relied on knowledge of crystal chemistry coupled with time-consuming materials synthesis with systematically varied elemental ratios2, 3. Computational methods have been developed to guide synthesis by predicting structures at specific compositions4, 5, 6 and predicting compositions for known crystal structures7, 8, with notable successes9, 10. However, the challenge of finding qualitatively new, experimentally realizable compounds, with crystal structures where the unit cell and the atom positions within it differ from known structures, remains for compositionally complex systems. Many valuable properties arise from substitution into known crystal structures, but materials discovery using this approach alone risks both missing best-in-class performance and attempting design with incomplete knowledge8, 11. Here we report the experimental discovery of two structure types by computational identification of the region of a complex inorganic phase field that contains them. This is achieved by computing probe structures that capture the chemical and structural diversity of the system and whose energies can be ranked against combinations of currently known materials. Subsequent experimental exploration of the lowest-energy regions of the computed phase diagram affords two materials with previously unreported crystal structures featuring unusual structural motifs. This approach will accelerate the systematic discovery of new materials in complex compositional spaces by efficiently guiding synthesis and enhancing the predictive power of the computational tools through expansion of the knowledge base underpinning them.
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Jun 2017
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I11-High Resolution Powder Diffraction
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Harry C.
Sansom
,
George F. S.
Whitehead
,
Matthew S.
Dyer
,
Marco
Zanella
,
Troy D.
Manning
,
Michael J.
Pitcher
,
Thomas J.
Whittles
,
Vinod R.
Dhanak
,
Jonathan
Alaria
,
John B.
Claridge
,
Matthew J.
Rosseinsky
Diamond Proposal Number(s):
[12336]
Open Access
Abstract: AgBiI4 powder, crystals and polycrystalline films were synthesized by sealed tube solid state reactions, chemical vapor transport (CVT) and solution processing, respectively, and their structural, optical and electronic properties are reported. The structure of AgBiI4 is based unambiguously upon a cubic close packed iodide sub-lattice, but it presents an unusual crystallographic problem: we show that the reported structure, a cubic defect-spinel, cannot be distinguished from a metrically cubic layered structure analogous to CdCl2 using either powder or single crystal X-ray crystallography. In addition, we demonstrate the existence a non-cubic CdCl2-type polymorph by isolation of non-twinned single crystals. The indirect optical band gap of AgBiI4 is measured to be 1.63(1) eV, comparable to the indirect band gap of 1.69(1) eV measured for BiI3 and smaller than that reported for other bismuth halides, suggesting that structures with a close-packed iodide sub-lattice may give narrower band gaps than those with perovskite structures. Band edge states closely resemble those of BiI3, however the p-type nature of AgBiI4 with low carrier concentration is more similar to MAPbI3 than the n-type BiI3. AgBiI4 shows good stability toward the AM1.5 solar spectrum when kept in a sealed environment, and is thermally stable below 90 °C.
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Jan 2017
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I11-High Resolution Powder Diffraction
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Abstract: We report neutron inelastic-scattering measurements on the stoichiometric iron-based superconductor LiFeAs. We find evidence for (i) magnetic scattering consistent with strong antiferromagnetic fluctuations and (ii) an increase in intensity in the superconducting state at low energies, similar to the resonant magnetic excitation observed in other iron-based superconductors. The results do not support a recent theoretical prediction of spin-triplet p-wave superconductivity in LiFeAs but instead suggest that the mechanism of superconductivity is similar to that in the other iron-based superconductors.
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Jun 2011
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I11-High Resolution Powder Diffraction
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Quinn D.
Gibson
,
Matthew S.
Dyer
,
Craig
Robertson
,
Charlene
Delacotte
,
Troy D.
Manning
,
Michael J.
Pitcher
,
Luke M.
Daniels
,
Marco
Zanella
,
Jonathan
Alaria
,
John B.
Claridge
,
Matthew
Rosseinsky
Diamond Proposal Number(s):
[17193]
Abstract: Here we report a new layered homologous series (Bi2O2Cu2−δSe2)mδ+(Bi2O2Se1−(m/n)δX (m/n)δ)nδ− (X = Cl, Br), composed of the known structural blocks BiOCuSe and Bi2O2Se. These structures are accessed by combining charge-compensating Cu vacancies and (Cl, Br) for Se substitution, in different layers. These new stacking homologoues have properties markedly different from those of the parent materials, and changing the layer stacking affects the properties including the band gap and thermal conductivity.
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Sep 2018
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I11-High Resolution Powder Diffraction
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Harry C.
Sansom
,
Leonardo R. V.
Buizza
,
Marco
Zanella
,
James T.
Gibbon
,
Michael
Pitcher
,
Matthew S.
Dyer
,
Troy D.
Manning
,
Vinod R.
Dhanak
,
Laura M.
Herz
,
Henry J.
Snaith
,
John B.
Claridge
,
Matthew J.
Rosseinsky
Open Access
Abstract: A newly reported compound, CuAgBiI5, is synthesized as powder, crystals, and thin films. The structure consists of a 3D octahedral Ag+/Bi3+ network as in spinel, but occupancy of the tetrahedral interstitials by Cu+ differs from those in spinel. The 3D octahedral network of CuAgBiI5 allows us to identify a relationship between octahedral site occupancy (composition) and octahedral motif (structure) across the whole CuI–AgI–BiI3 phase field, giving the ability to chemically control structural dimensionality. To investigate composition–structure–property relationships, we compare the basic optoelectronic properties of CuAgBiI5 with those of Cu2AgBiI6 (which has a 2D octahedral network) and reveal a surprisingly low sensitivity to the dimensionality of the octahedral network. The absorption onset of CuAgBiI5 (2.02 eV) barely changes compared with that of Cu2AgBiI6 (2.06 eV) indicating no obvious signs of an increase in charge confinement. Such behavior contrasts with that for lead halide perovskites which show clear confinement effects upon lowering dimensionality of the octahedral network from 3D to 2D. Changes in photoluminescence spectra and lifetimes between the two compounds mostly derive from the difference in extrinsic defect densities rather than intrinsic effects. While both materials show good stability, bulk CuAgBiI5 powder samples are found to be more sensitive to degradation under solar irradiation compared to Cu2AgBiI6.
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Nov 2021
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I11-High Resolution Powder Diffraction
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Michael J.
Pitcher
,
Tom
Lancaster
,
Jack D.
Wright
,
Isabel
Franke
,
Andrew
Steele
,
Peter J.
Baker
,
Francis L.
Pratt
,
William
Trevelyan Thomas
,
Dinah R.
Parker
,
Stephen J.
Blundell
,
Simon J.
Clarke
Abstract: The response of the superconducting state and crystal structure of LiFeAs to chemical substitutions on both the Li and the Fe sites has been probed using high-resolution X-ray and neutron diffraction measurements, magnetometry, and muon-spin rotation spectroscopy. The superconductivity is extremely sensitive to composition: Li-deficient materials (Li1−yFe1+yAs with Fe substituting for Li) show a very rapid suppression of the superconducting state, which is destroyed when y exceeds 0.02, echoing the behavior of the Fe1+ySe system. Substitution of Fe by small amounts of Co or Ni results in monotonic lowering of the superconducting transition temperature, Tc, and the superfluid stiffness, ρs, as the electron count increases. Tc is lowered monotonically at a rate of 10 K per 0.1 electrons added per formula unit irrespective of whether the dopant is Co and Ni, and at higher doping levels superconductivity is completely suppressed. These results and the demonstration that the superfluid stiffness in these LiFeAs-derived compounds is higher than in all of the iron pnictide materials underlines the unique position that LiFeAs occupies in this class.
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Jul 2010
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I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[9282]
Abstract: Calculation of the energetics of aliovalent substitution into the olivine LiMgPO4 suggests that replacement of Mg2+ by In3+ is the most effective way to introduce lithium vacancies and thus generate Li ion conductivity. Experimental synthesis accesses materials with up to 17% Li vacancy content. An order-of-magnitude increase in the high-temperature hopping rates probed by 7Li NMR spin–lattice relaxation, and over 2 orders of magnitude increase in the room-temperature Li+ ion conductivity measured by impedance spectroscopy is observed upon the introduction of In3+ ions and Li vacancies. NMR spectroscopy and calculations reveal that the energy barrier to site-to-site hopping is 0.3–0.5 eV, comparable with best-in-class nonoxide systems such as argyrodite, but NMR-derived hopping rates, and impedance spectroscopy shows that longer range transport is less facile with activation energies in the range of 0.7–1 eV. Calculations suggest that this is because the Li vacancies are strongly bound to the In3+ dopants, suggesting that high lithium mobilities in oxides are accessible but high conductivities require strategies to separate defect from dopant.
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Feb 2015
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I11-High Resolution Powder Diffraction
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Christos A.
Tzitzeklis
,
Jyoti K.
Gupta
,
Matthew S.
Dyer
,
Troy D.
Manning
,
Michael J.
Pitcher
,
Hongjun J.
Niu
,
Stanislav
Savvin
,
Jonathan
Alaria
,
George R.
Darling
,
John B.
Claridge
,
Matthew J.
Rosseinsky
Diamond Proposal Number(s):
[12336]
Abstract: It is challenging to achieve p-type doping of zinc oxides (ZnO), which are of interest as transparent conductors in optoelectronics. A ZnO-related ternary compound, SrZnO2, was investigated as a potential host for p-type conductivity. First-principles investigations were used to select from a range of candidate dopants the substitution of Li+ for Zn2+ as a stable, potentially p-type, doping mechanism in SrZnO2. Subsequently, single-phase bulk samples of a new p-type-doped oxide, SrZn1–xLixO2 (0 < x < 0.06), were prepared. The structural, compositional, and physical properties of both the parent SrZnO2 and SrZn1–xLixO2 were experimentally verified. The band gap of SrZnO2 was calculated using HSE06 at 3.80 eV and experimentally measured at 4.27 eV, which confirmed the optical transparency of the material. Powder X-ray diffraction and inductively coupled plasma analysis were combined to show that single-phase ceramic samples can be accessed in the compositional range x < 0.06. A positive Seebeck coefficient of 353(4) μV K–1 for SrZn1–xLixO2, where x = 0.021, confirmed that the compound is a p-type conductor, which is consistent with the pO2 dependence of the electrical conductivity observed in all SrZn1–xLixO2 samples. The conductivity of SrZn1–xLixO2 is up to 15 times greater than that of undoped SrZnO2 (for x = 0.028 σ = 2.53 μS cm–1 at 600 °C and 1 atm of O2).
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Sep 2018
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I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[9282]
Open Access
Abstract: A room temperature magnetoelectric multiferroic is of interest as, e.g., magnetoelectric random access memory. Bulk samples of the perovskite (1−x)BiTi(1−y)/2FeyMg(1−y)/2O3–xCaTiO3 (BTFM–CTO) are simultaneously ferroelectric, weakly ferromagnetic, and magnetoelectric at room temperature. In BTFM–CTO, the volatility of bismuth oxide, and the complex subsolidus reaction kinetics, cause the formation of a microscopic amount of ferrimagnetic spinel impurity, which complicates the quantitative characterization of their intrinsic magnetic and magnetoelectric properties. Here, a controlled synthesis route to single-phase bulk samples of BTFM–CTO is devised and their intrinsic properties are determined. For example, the composition x = 0.15, y = 0.75 shows a saturated magnetization of 0.0097μB per Fe, a linear magnetoelectric susceptibility of 0.19(1) ps m−1, and a polarization of 66 μC cm−2 at room temperature. The onset of weak ferromagnetism and linear magnetoelectric coupling are shown to coincide with the onset of bulk long-range magnetic order by neutron diffraction. The synthesis strategy developed here will be invaluable as the phase diagram of BTFM–CTO is explored further, and as an example for the synthesis of other compositionally complex BiFeO3-related materials.
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Feb 2016
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