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Oriano
Francescangeli
,
Vesna
Stanic
,
Sofia
Torgova
,
Alfredo
Strigazzi
,
Nicola
Scaramuzza
,
Claudio
Ferrero
,
Igor
Dolbnya
,
Thomas
Weiss
,
Roberto
Berardi
,
Luca
Muccioli
,
Silvia
Orlandi
,
Claudio
Zannoni
Abstract: The still undiscovered fluid ferroelectric nematic phase is expected to exhibit a much faster and easier response to an external electric field compared to conventional ferroelectric smectic liquid crystals; therefore, the discovery of such a phase could open new avenues in electro-optic device technology. Here, experimental evidence of a ferroelectric response to a switching electric field in a low molar mass nematic liquid crystal is reported and connected with field-induced biaxiality. The fluid is made of bent-core polar molecules and is nematic over a range of 120 °C. Combining repolarization current measurements, electro-optical characterizations, X-ray diffraction and computer simulations, ferroelectric switching is demonstrated and it is concluded that the response is due to field-induced reorganization of polar cybotactic groups within the nematic phase. This work represents significant progress toward the realization of ferroelectric fluids that can be aligned at command with a simple electric field.
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Aug 2009
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Abstract: Combinatorial atmospheric pressure chemical vapor deposition (APCVD) is used to deposit anatase TiO2 with a graded level of F-doping between 1.10 ≤ F:Ti (at%) ≤ 2.57 from the reaction of titanium tetrachloride, ethyl acetate and trifluoroacetic acid at 500 °C on glass. The photocatalytic activity and electrical resistivity of 200 allotted positions across a grid are screened using high-throughput techniques. A blue region of film is singled out for containing the lowest electrical resistivities of any previously reported doped or undoped TiO2-based system formed by APCVD (ρ ≈ 0.22–0.45 Ω cm, n = 0.8–1.2 × 1018 cm−3, μ = 18–33 cm2 V−1 s−1). The blue region contains a lower fluorine doping level (F:Ti ≈ 1.1–1.6%, Ebg ≈ 3.06 eV) than its neighboring colorless region (F:Ti ≈ 2.3–2.6%, Ebg ≈ 3.15–3.21 eV, ρ ≈ 0.61–1.3 Ω cm). State-of-the-art hybrid density functional theory calculations were employed to elucidate the nature of the different doping behaviors. Two distinct fluorine doping environments were present. At low concentrations, F substituting for O (FO) dominates, forming blue F:TiO2. At high concentrations, negatively charged fluorine interstitials (Fi−1) begin to dominate, forming transparent F:TiO2.
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Mar 2014
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Jack E. N.
Swallow
,
Benjamin A. D.
Williamson
,
Thomas J.
Whittles
,
Max
Birkett
,
Thomas J.
Featherstone
,
Nianhua
Peng
,
Alex
Abbott
,
Mark
Farnworth
,
Kieran J.
Cheetham
,
Paul
Warren
,
David O.
Scanlon
,
Vin R.
Dhanak
,
Tim D.
Veal
Open Access
Abstract: The factors limiting the conductivity of fluorine-doped tin dioxide (FTO) produced via atmospheric pressure chemical vapor deposition are investigated. Modeling of the transport properties indicates that the measured Hall effect mobilities are far below the theoretical ionized impurity scattering limit. Significant compensation of donors by acceptors is present with a compensation ratio of 0.5, indicating that for every two donors there is approximately one acceptor. Hybrid density functional theory calculations of defect and impurity formation energies indicate the most probable acceptor-type defects. The fluorine interstitial defect has the lowest formation energy in the degenerate regime of FTO. Fluorine interstitials act as singly charged acceptors at the high Fermi levels corresponding to degenerately n-type films. X-ray photoemission spectroscopy of the fluorine impurities is consistent with the presence of substitutional FO donors and interstitial Fi in a roughly 2:1 ratio in agreement with the compensation ratio indicated by the transport modeling. Quantitative analysis through Hall effect, X-ray photoemission spectroscopy, and calibrated secondary ion mass spectrometry further supports the presence of compensating fluorine-related defects.
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Nov 2017
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Zilu
Liu
,
Tianjun
Liu
,
Christopher N.
Savory
,
José P.
Jurado
,
Juan Sebastián
Reparaz
,
Jianwei
Li
,
Long
Pan
,
Charl F. J.
Faul
,
Ivan P.
Parkin
,
Gopinathan
Sankar
,
Satoru
Matsuishi
,
Mariano
Campoy‐quiles
,
David O.
Scanlon
,
Martijn A.
Zwijnenburg
,
Oliver
Fenwick
,
Bob C.
Schroeder
Open Access
Abstract: Organometallic coordination polymers (OMCPs) are a promising class of thermoelectric materials with high electrical conductivities and thermal resistivities. The design criteria for these materials, however, remain elusive and so far material modifications have been focused primarily on the nature of the metal cation to tune the thermoelectric properties. Herein, an alternative approach is described by synthesizing new organic ligands for OMCPs, allowing modulation of the thermoelectric properties of the novel OMCP materials over several orders of magnitude, as well as controlling the polarity of the Seebeck coefficient. Extensive material purification combined with spectroscopy experiments and calculations furthermore reveal the charge‐neutral character of the polymer backbones. In the absence of counter‐cations, the OMCP backbones are composed of air‐stable, ligand‐centered radicals. The findings open up new synthetic possibilities for OMCPs by removing structural constraints and putting significant emphasis on the molecular structure of the organic ligands in OMCP materials to tune their thermoelectric properties.
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Jun 2020
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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.
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May 2014
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Abstract: Quasi-1D nanochains of spherical magnetic ferrite particles with a homogeneous particle size of ≈200 nm and a micrometer-sized chain length are fabricated via a self-assembly method under an external magnetic field. This assisting magnetic field (H_assist), applied during synthesis, significantly modifies the distribution of the Fe2+ Oh, Fe3+ Td, and Fe3+ Oh cations in the chains, as demonstrated by X-ray magnetic circular dichroism (XMCD) combined with theoretical analysis. This provides direct evidence of the nontrivial role of external synthetic conditions for defining the crystal chemistry of nanoscale ferrites and in turn their magnetic properties, providing an extra degree of freedom for intentional control over the performances of 1D magnetic nanodevices for various applications. Magnetic imaging, performed via XMCD in photoemission electron microscopy, further shows the possibility of creating and trapping a series of adjacent magnetic domain walls in a single chain, suggesting that there is great application potential for these nanochains in 1D magnetic nanodevices, as determined by field- or currentdriven domain wall motions. Practical control over the magnetic properties of the nanochains is also achieved by extrinsic dopants of cobalt and zinc, which are observed to occupy the ferrite ionic sites in a selective manner.
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May 2017
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B18-Core EXAFS
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Abstract: Amorphous calcium carbonate (ACC) is an important intermediate in the formation of crystalline CaCO3 biominerals, where its crystallization is controlled using soluble additives. However, although this transformation often occurs in the solid state, experiments mainly focus on the effect of additives on ACC crystallization in solution. This paper addresses this issue and compares the crystallization, in solution and in the solid state, of ACC precipitated in the presence of a range of additives. Surprisingly, these results show that some additives exhibit a Janus behavior, where they retard crystallization in solution, yet accelerate it in the solid state. This is observed for all of the larger molecules examined, while the small molecules retard crystallization in both solution and the solid state.
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Oct 2012
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B18-Core EXAFS
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Davinder
Bhachu
,
Sanjay
Sathasivam
,
Gopinathan
Sankar
,
David O.
Scanlon
,
Giannantonio
Cibin
,
Claire J.
Carmalt
,
Ivan
Parkin
,
Graeme W.
Watson
,
Salem M.
Bawaked
,
Abdullah Y.
Obaid
,
Shaeel
Al-thabaiti
,
Sulaiman N.
Basahel
Diamond Proposal Number(s):
[8071]
Abstract: This paper reports the synthesis of highly conductive niobium doped titanium dioxide (Nb:TiO2) films from the decomposition of Ti(OEt)4 with dopant quantities of Nb(OEt)5 by aerosol-assisted chemical vapor deposition (AACVD). Doping Nb into the Ti sites results in n-type conductivity, as determined by Hall effect measurements. The doped films display significantly improved electrical properties compared to pristine TiO2 films. For 5 at.% Nb in the films, the charge carrier concentration was 2 × 1021 cm?3 with a mobility of 2 cm2 V–1 s–1 . The corresponding sheet resistance is as low as 6.5 ? sq–1 making the films suitable candidates for transparent conducting oxide (TCO) materials. This is, to the best of our knowledge, the lowest reported sheet resistance for Nb:TiO2 films synthesized by vapour deposition. The doped films are also blue in colour, with the intensity dependent on the Nb concentration in the films. A combination of synchrotron, laboratory and theoretical techniques confirmed niobium doping into the anatase TiO2 lattice. Computational methods also confirmed experimental results of both delocalized (Ti4+) and localized polaronic states (Ti3+) states. Additionally, the doped films also functioned as photocatalysts. Thus, Nb:TiO2 combines four functional properties (photocatalysis, electrical conductivity, optical transparency and blue colouration) within the same layer, making it a promising alternative to conventional TCO materials.
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Aug 2014
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B18-Core EXAFS
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Open Access
Abstract: Lithium‐rich transition metal cathodes can deliver higher capacities than stoichiometric materials by exploiting redox reactions on oxygen. However, oxidation of O2− on charging often results in loss of oxygen from the lattice. In the case of Li2MnO3 all the capacity arises from oxygen loss, whereas doping with Ni and/or Co leads to the archetypal O‐redox cathodes Li[Li0.2Ni0.2Mn0.6]O2 and Li[Li0.2Ni0.13Co0.13Mn0.54]O2, which exhibit much reduced oxygen loss. Understanding the factors that determine the degree of reversible O‐redox versus irreversible O‐loss is important if Li‐rich cathodes are to be exploited in next generation lithium‐ion batteries. Here it is shown that the almost complete eradication of O‐loss with Ni substitution is due to the presence of a less Li‐rich, more Ni‐rich (nearer stoichiometric) rocksalt shell at the surface of the particles compared with the bulk, which acts as a self‐protecting layer against O‐loss. In the case of Ni and Co co‐substitution, a thinner rocksalt shell forms, and the O‐loss is more abundant. In contrast, Co doping does not result in a surface shell yet it still suppresses O‐loss, although less so than Ni and Ni/Co doping, indicating that doping without shell formation is effective and that two mechanisms exist for O‐loss suppression.
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Aug 2020
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B18-Core EXAFS
I15-1-X-ray Pair Distribution Function (XPDF)
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Diamond Proposal Number(s):
[16168, 16460]
Abstract: Perovskite‐like NaNbO3‐Bi1/3NbO3 solid solutions are studied to understand the interactions between octahedral rotations, which dominate the structural behavior of NaNbO3 and displacive disorder of Bi present in Bi1/3NbO3. Models of instantaneous structures for representative compositions are obtained by refining atomic coordinates against X‐ray total scattering and extended X‐ray‐absorption fine structure data, with additional input obtained from transmission electron microscopy. A mixture of distinct cations and vacancies on the cuboctahedral A‐sites in Na1−3x Bix NbO3 (x ≤ 0.2) results in 3D nanoscale modulations of structural distortions. This phenomenon is determined by the inevitable correlations in the chemical composition of adjacent unit cells according to the structure type—an intrinsic property of any nonmolecular crystals. Octahedral rotations become suppressed as x increases. Out‐of‐phase rotations vanish for x > 0.1, whereas in‐phase tilts persist up to x = 0.2, although for this composition their correlation length becomes limited to the nanoscale. The loss of out‐of‐phase tilting is accompanied by qualitative changes in the probability density distributions for Bi and Nb, with both species becoming disordered over loci offset from the centers of their respective oxygen cages. Symmetry arguments are used to attribute this effect to different strengths of the coupling between the cation displacements and out‐of‐phase versus in‐phase rotations. The displacive disorder of Bi and Nb combined with nanoscale clustering of lattice distortions are primarily responsible for the anomalous broadening of the temperature dependence of the dielectric constant.
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Jun 2020
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