“Formation of a complete solid solution between the triphylite and fayalite olivine structures”. Recham N, Casas-Cabanas M, Cabana J, Grey CP, Jumas J-C, Dupont L, Armand M, Tarascon J-M, Chemistry of materials 20, 6798 (2008). http://doi.org/10.1021/cm801817n
Abstract: The recent infatuation for LiFePO4 as positive electrode material in Li-ion batteries has prompted a renewed interest in olivine-type structures, with a view to enhance their conduction proper-ties. We show that the dual substitution of Li for Fe and of P for Si in the olivine LiFePO4 phase leads to a complete solid solution Li1-xFe1+xP1-xSixO4 as deduced from combined X-ray diffraction, Mossbauer, and NMR experiments. Our findings challenge the common belief that the anionic network cannot be substituted. Moreover. it is found that such a substitution promotes Li intersite mixing between the olivine M1 and M2 sites. Such mixing, together with the worsening of the conducting properties of the dually substituted samples, is believed to be responsible for the poor electrochemical performances of the member's series. Beyond x = 0.20, the samples were electrochemically inactive. While the current materials are disappointing application-wise, such a study provides clues to the rich chemistry remaining to be unveiled with olivine-type structures in particular and polyanionic compounds in general.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 35
DOI: 10.1021/cm801817n
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“Incommensurate modulation and luminescence in the CaGd2(1-x)Eu2x(MoO4)4(1-y)(WO)4y (0\leq x\leq1, 0\leq y\leq1) red phosphors”. Morozov VA, Bertha A, Meert KW, Van Rompaey S, Batuk D, Martinez GT, Van Aert S, Smet PF, Raskina MV, Poelman D, Abakumov AM, Hadermann J;, Chemistry of materials 25, 4387 (2013). http://doi.org/10.1021/cm402729r
Abstract: Scheelite related compounds (A',A '') [(B',B '')O-4], with B', B '' = W and/or Mo are promising new light-emitting materials for photonic applications, including phosphor converted LEDs (light-emitting diodes). In this paper, the creation and ordering of A-cation vacancies and the effect of cation substitutions in the scheelite-type framework are investigated as a factor for controlling the scheelite-type structure and luminescent properties. CaGd2(1-x)Eu2x(MoO4)(4(1-y))(WO4)(4y) (0 <= x <= 1, 0 <= y <= 1) solid solutions with scheelite-type structure were synthesized by a solid state method, and their structures were investigated using a combination of transmission electron microscopy techniques and powder X-ray diffraction. Within this series all complex molybdenum oxides have (3 + 2)D incommensurately modulated structures with superspace group I4(1)/a(alpha,beta,0)00(-beta,alpha,0)00, while the structures of all tungstates are (3 + 1)D incommensurately modulated with superspace group I2/b(alpha beta 0)00. In both cases the modulation arises because of cation-vacancy ordering at the A site. The prominent structural motif is formed by columns of A-site vacancies running along the c-axis. These vacant columns occur in rows of two or three aligned along the [110] direction of the scheelite subcell. The replacement of the smaller Gd3+ by the larger Eu3+ at the A-sublattice does not affect the nature of the incommensurate modulation, but an increasing replacement of Mo6+ by W6+ switches the modulation from (3 + 2)D to (3 + 1)D regime. Thus, these solid solutions can be considered as a model system where the incommensurate modulation can be monitored as a function of cation nature while the number of cation vacancies at the A sites remain constant upon the isovalent cation replacement. All compounds' luminescent properties were measured, and the optical properties were related to the structural properties of the materials. CaGd2(1-x)(MoO4)(4(1-y))(WO4)(4y) phosphors emit intense red light dominated by the D-5(0)-F-7(2) transition at 612 nm, along with other transitions from the D-5(1) and D-5(0) excited states. The intensity of the 5D0-7F2 transition reaches a maximum at x = 0.5 for y = 0 and 1.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 63
DOI: 10.1021/cm402729r
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“Indifference of superconductivity and magnetism to size-mismatched cations in the layered iron arsenides Ba1-xNaxFe2As2”. Cortes-Gil R, Parker DR, Pitcher MJ, Hadermann J, Clarke SJ, Chemistry of materials 22, 4304 (2010). http://doi.org/10.1021/cm100956k
Abstract: The evolution of the structure, magnetic ordering, and superconductivity in the series Ba(1-x)Na(x)Fe(2)As(2) is reported up to the limiting Na-rich composition with x = 0.6; the more Na-rich compositions are unstable at high temperatures with respect to competing phases. The magnetic and superconducting behaviors of the Bai,Na,Fe,As, members are similar to those of the betterinvestigated Ba(1-x)Na(x)Fe(2)As(2) analogues. This is evidently a consequence of the quantitatively similar evolution of the structure of the FeAs layers in the two series. In Ba(1-x)Na(x)Fe(2)As(2) antiferromagnetic order and an associated structural distortion are evident for x <= 0.35 and superconductivity is evident when x exceeds 0.2. For 0.4 <= x <= 0.6 bulk superconductivity is evident, and the long-range antiferromagnetically ordered state is completely suppressed. The maximum T(c) in the Ba(1-x)Na(x)Fe(2)As(2) series, as judged by the onset of diamagnetism, is 34K in Ba(0.6)Na(0.4)Fe(2)As(2). Despite the large mis-match in sizes between the two electropositive cations which separate the FeAs layers, there is no evidence for ordering of these cations on the length scale probed by electron diffraction.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 31
DOI: 10.1021/cm100956k
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“Iron catalysts for the growth of carbon nanofibers : Fe, Fe3C or both?”.He Z, Maurice J-L, Gohier A, Lee CS, Pribat D, Cojocaru CS, Chemistry of materials 23, 5379 (2011). http://doi.org/10.1021/cm202315j
Abstract: Iron is a widely used catalyst for the growth of carbon nanotubes (CNTs) or carbon nanofibers (CNFs) by catalytic chemical vapor deposition. However, both Fe and FeC compounds (generally, Fe3C) have been found to catalyze the growth of CNTs/CNFs, and a comparison study of their respective catalytic activities is still missing. Furthermore, the control of the crystal structure of iron-based catalysts, that is α-Fe or Fe3C, is still a challenge, which not only obscures our understanding of the growth mechanisms of CNTs/CNFs, but also complicates subsequent procedures, such as the removal of catalysts for better industrial applications. Here, we show a partial control of the phase of iron catalysts (α-Fe or Fe3C), obtained by varying the growth temperatures during the synthesis of carbon-based nanofibers/nanotubes in a plasma-enhanced chemical vapor deposition reactor. We also show that the structure of CNFs originating from Fe3C is bamboo-type, while that of CNFs originating from Fe is not. Moreover, we directly compare the growth rates of carbon-based nanofibers/nanotubes during the same experiments and find that CNFs/CNTs grown by α-Fe nanoparticles are longer than CNFs grown from Fe3C nanoparticles. The influence of the type of catalyst on the growth of CNFs is analyzed and the corresponding possible growth mechanisms, based on the different phases of the catalysts, are discussed.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 91
DOI: 10.1021/cm202315j
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“A layered iron-rich 2234-type with a mixed valence of iron: the ferrimagnetic Tl-doped Fe2(Sr2-\varepsilonTl\varepsilon)Sr3Fe4O14.65”. Lepoittevin C, Malo S, Nguyen N, Hebert S, Van Tendeloo G, Hervieu M, Chemistry of materials 20, 6468 (2008). http://doi.org/10.1021/cm8014385
Abstract: A new Tl-doped strontium ferrite Fe2(Sr2-Tl)Sr3Fe4O14.65, with an original structure, has been synthesized and structurally characterized by powder X-ray diffraction and transmission electron microscopy. The TGA and Mssbauer studies evidence a mixed valence of iron. The structure exhibits a commensurate modulation, with a F-type subcell a ≈ b ≈ 5.4 Å (≈ ap√2), c ≈ 42 Å with a modulation vector q = αa* with α = 0.4. The supercell parameters have been refined as a= 27.1101(8) Å, b= 5.5187(2) Å and c= 42.0513(9) Å, in the space group Fmmm. The electron diffraction and electron microscopy data of this novel ferrite show that it can be described as a FeTl-2234-type structure corresponding to the intergrowth of a quadruple perovskite slice [(SrFeO2.8)4], with a complex rock salt related slice [Fe2(Sr2-Tl)O3.4]∞, built up of one double iron layer [Fe2O2.4] sandwiched between two [SrO] layers. The HRTEM images show that the oxygen atoms and vacancies are randomly distributed in the perovskite layers while the HAADF STEM images evidence the absence of Tl segregation in the matrix. Fe2(Sr2-Tl)Sr3Fe4O14.65 exhibits a very large value of χ (11emu/mol) at 5 K, which remains large at 400 K; the M(H) loop presents a shape characteristic of ferrimagnetism, with a large coercive field of 0.3 T. The value of magnetization saturates at 400 K at 0.68 μB/Fe. At 10 K, the value of magnetization reaches a maximum of 2 μB/Fe. The resistivity presents a semiconducting-like behavior, with ρ 800 Ω·cm at 300 K.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 8
DOI: 10.1021/cm8014385
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“Layered oxychlorides [PbBiO2]An+1BnO3n-1Cl2(A = Pb/Bi, B = Fe/Ti) : intergrowth of the hematophanite and sillen phases”. Batuk M, Batuk D, Tsirlin AA, Filimonov DS, Sheptyakov DV, Frontzek M, Hadermann J, Abakumov AM, Chemistry of materials 27, 2946 (2015). http://doi.org/10.1021/acs.chemmater.5b00233
Abstract: New layered structures corresponding to the general formula [PbBiO2]A(n+1)B(n)O(3n-1)Cl(2) Were prepared. Pb5BiFe3O10Cl2 (n = 3) and Pb5Bi2Fe4O13Cl2 (n = 4) are built as a stacking of truncated A(n+1)B(n)O(3n-1) perovskite blocks and alpha-PbO-type [A(2)O(2)](2+) (A = Pb, Bi) blocks combined with chlorine sheets. The alternation of these structural blocks can be represented as an intergrowth between the hematophanite and Sullen-type structural blocks. The crystal and-Magnetic structures of Pb5BiFe3O10Cl2 and Pb5Bi2Fe4O13Cl2 were investigated in the temperature range of 1.5-700 K using X-ray and neutron powder diffraction, transmission electron microscopy and Fe-57 Mossbauer spectroscopy. Both compounds crystallize in the I4/mmm space group with the unit cell parameters a approximate to a(p) approximate to 3.92 angstrom (a unit-cell parameter of the perovskite-structure), c approximate to 43.0 angstrom for the n = 3 member and c approximate to 53.5 angstrom for the n = 4 member. Despite the large separation between the slabs containing the Fe3+ ions (nearly 14 angstrom), long-range antiferromagnetic order sets in below similar to 600 K with the G-type arrangement of the Fe magnetic moments aligned along the c-axis. The possibility of mixing d(0) and d(n) cations at the B sublattice of these structures was also demonstrated by preparing the Ti-substituted n = 4 member Pb6BiFe3TiO13Cl2.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 11
DOI: 10.1021/acs.chemmater.5b00233
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“Local oxygen-vacancy ordering and twinned octahedral tilting pattern in the Bi0.81Pb0.19FeO2.905 cubic perovskite”. Dachraoui W, Hadermann J, Abakumov AM, Tsirlin AA, Batuk D, Glazyrin K, McCammon C, Dubrovinsky L, Van Tendeloo G, Chemistry of materials 24, 1378 (2012). http://doi.org/10.1021/cm300178x
Abstract: The structure of Bi0.81Pb0.19FeO2.905 was investigated on different length scales using a combination of electron diffraction, high-resolution scanning transmission electron microscopy, synchrotron X-ray powder diffraction, and Mössbauer spectroscopy. In the 80300 K temperature range, the average crystal structure of Bi0.81Pb0.19FeO2.905 is a cubic Pm3̅m perovskite with a = 3.95368(3) Å at T = 300 K. The (Pb2+, Bi3+) cations and O2 anions are randomly displaced along the 110 cubic directions, indicating the steric activity of the lone pair on the Pb2+ and Bi3+ cations and a tilting distortion of the perovskite framework. The charge imbalance induced by the heterovalent Bi3+ → Pb2+ substitution is compensated by the formation of oxygen vacancies preserving the trivalent state of the Fe cations. On a short scale, oxygen vacancies are located in anion-deficient (FeO1.25) layers that are approximately 6 perovskite unit cells apart and transform every sixth layer of the FeO6 octahedra into a layer with a 1:1 mixture of corner-sharing FeO4 tetrahedra and FeO5 tetragonal pyramids. The anion-deficient layers act as twin planes for the octahedral tilting pattern of adjacent perovskite blocks. They effectively randomize the octahedral tilting and prevent the cooperative distortion of the perovskite framework. The disorder in the anion sublattice impedes cooperative interactions of the local dipoles induced by the off-center displacements of the Pb and Bi cations. Magnetic susceptibility measurements evidence the antiferromagnetic ordering in Bi0.81Pb0.19FeO2.905 at low temperatures.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 27
DOI: 10.1021/cm300178x
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“Microwave-assisted bromination of double-walled carbon nanotubes”. Colomer J-F, Marega R, Traboulsi H, Meneghetti M, Van Tendeloo G, Bonifazi D, Chemistry of materials 21, 4747 (2009). http://doi.org/10.1021/cm902029m
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 46
DOI: 10.1021/cm902029m
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“Multiple twinning as a structure directing mechanism in layered rock-salt-type oxides : NaMnO2 polymorphism, redox potentials, and magnetism”. Abakumov AM, Tsirlin AA, Bakaimi I, Van Tendeloo G, Lappas A, Chemistry of materials 26, 3306 (2014). http://doi.org/10.1021/cm5011696
Abstract: New polymorphs of NaMnO2 have been observed using transmission electron microscopy and synchrotron X-ray powder diffraction. Coherent twin planes confined to the (NaMnO2) layers, parallel to the (10 (1) over bar) crystallographic planes of the monoclinic layered rock-salt-type alpha-NaMnO2 (O3) structure, form quasi-periodic modulated sequences, with the known alpha-and beta-NaMnO2 polymorphs as the two limiting cases. The energy difference between the polymorphic forms, estimated using a DFT-based structure relaxation, is on the scale of the typical thermal energies that results in a high degree of stacking disorder in these compounds. The results unveil the remarkable effect of the twin planes on both the magnetic and electrochemical properties. The polymorphism drives the magnetic ground state from a quasi-1D spin system for the geometrically frustrated alpha-polymorph through a two-leg spin ladder for the intermediate stacking sequence toward a quasi-2D magnet for the beta-polymorph. A substantial increase of the equilibrium potential for Na deintercalation upon increasing the concentration of the twin planes is calculated, providing a possibility to tune the electrochemical potential of the layered rock-salt ABO(2) cathodes by engineering the materials with a controlled concentration of twins.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 35
DOI: 10.1021/cm5011696
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“Novel, oxygen-deficient n=3 RP-member Sr3NdFe3O9-\delta and its topotactic derivatives”. Pelloquin D, Hadermann J, Giot M, Caignaert V, Michel C, Hervieu M, Raveau B, Chemistry of materials 16, 1715 (2004). http://doi.org/10.1021/cm030351n
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 24
DOI: 10.1021/cm030351n
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“Off-stoichiometry effects on the crystalline and defect structure of hexagonal manganite REMnO3 films (RE = Y, Er, Dy)”. Gélard J, Jehanathan N, Roussel H, Gariglio S, Lebedev OI, Van Tendeloo G, Dubourdieu C, Chemistry of materials 23, 1232 (2011). http://doi.org/10.1021/cm1029358
Abstract: The crystalline and defect structure of epitaxial hexagonal RExMnyO3 (RE = Er, Dy) films with varying cationic composition was investigated by X-ray diffraction and transmission electron microscopy. The films are composed of a strained layer at the interface with the substrate and of a relaxed layer on top of it. The critical thickness is of 10 to 25 nm. For Mn-rich films (or RE deficient), an off-stoichiometric composition maintaining the hexagonal LuMnO3-type structure is stabilized over a large range of the RE/Mn ratio (0.72−1.00), with no Mn-rich secondary phases observed. A linear dependence of the out-of-plane lattice parameter with RE/Mn is observed in this range. Out-of-phase boundary (OPB) extended defects are observed in all films and exhibit a local change in stoichiometry. Such a large solubility limit in the RE deficient region points toward the formation of vacancies on the RE site (RExMnO3−δ, with 0.72 ≤ x < 1), a phenomenon that is encountered in perovskite manganites such as LaxMnO3−δ (x < 1) and that may strongly impact the physical properties of hexagonal manganites.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 17
DOI: 10.1021/cm1029358
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“Oxygen vacancy ordering in the double-layered Ruddlesden-Popper cobaltite Sm2BaCo2O7-\delta”. Gillie LJ, Hadermann J, Hervieu M, Maignan A, Martin C, Chemistry of materials 20, 6231 (2008). http://doi.org/10.1021/cm8010138
Abstract: A new oxygen-deficient Ruddlesden−Popper (RP) cobaltite Sm2BaCo2O7−δ (δ ≈ 1.0) has been synthesized and the crystal structure elucidated by Rietveld analysis of X-ray powder diffraction (XRD) data and transmission electron microscopy (TEM). The phase crystallizes in a primitive orthorhombic unit cell, with lattice parameters a = 5.4371(4) Å; b = 5.4405(4) Å and c = 19.8629(6) Å, and space group Pnnm. Contrary to other oxygen-deficient cobalt RP phases, the oxygen vacancies are located in the equatorial positions of the [CoO] layers to give an intralayer structure similar to Sr2Mn2O5, which is not usually observed for cobalt-containing materials. The Sm3+ and Ba2+ cations show a strong preference for distinct sites, with the majority of the larger Ba2+ cations situated in the perovskite block layers and Sm3+ cations predominantly in the rock salt layers. Magnetic susceptibility data demonstrate the strong antiferromagnetic (AFM) character of Sm2BaCo2O7−δ.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 7
DOI: 10.1021/cm8010138
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“Physicochemical and structural characterization of mesoporous aluminosilicates synthesized from leached saponite with additional aluminum incorporation”. Linssen T, Cassiers K, Cool P, Lebedev O, Whittaker A, Vansant EF, Chemistry of materials 15, 4863 (2003). http://doi.org/10.1021/cm031111a
Abstract: A thorough investigation was performed on the physical (mechanical, thermal, and hydrothermal stability) and chemical (ion exchange capacity and silanol number) characteristics of aluminosilicate FSMs, synthesized via a new successful short-time synthesis route using leached saponite and a low concentration of CTAB. Moreover, the influence of an additional Al incorporation, utilizing different aluminum sources, on the structure of the FSM derived from saponite is studied. A mesoporous aluminosilicate with a low Si/Al ratio of 12.8 is synthesized, and still has a very large surface area of 1130 m(2)/g and pore volume of 0.92 cm(3)/g. The aluminum-containing samples all have a high cation exchange capacity of around 1 mmol/9 while they still have a silanol number of about 0.9 OH/nm(2); both characteristics being interesting for high-yield postsynthesis modification reactions. Finally, a study is performed on the transformation of the aluminosilicates into their Bronsted acid form via the exchange with ammonium ions and a consecutive heat treatment.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT); Laboratory of adsorption and catalysis (LADCA)
Impact Factor: 9.466
Times cited: 11
DOI: 10.1021/cm031111a
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“Positional and orientational disorder in a solid solution of Sr9-xNi1.5-x(PO4)7 (x=0.3)”. Belik A, Izumi F, Ikeda T, Morozov VA, Dilanian R, Torii S, Kopnin E, Lebedev OI, Van Tendeloo G, Lazoryak BI, Chemistry and materials 14, 4464 (2002). http://doi.org/10.1021/cm0206901
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 28
DOI: 10.1021/cm0206901
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“Reply to Comment on “Frustrated octahedral tilting distortion in the incommensurately modulated Li3xNd2/3-xTiO3 perovskites””. Abakumov AM, Erni R, Tsirlin AA, Chemistry of materials 26, 1288 (2014). http://doi.org/10.1021/cm500005d
Keywords: Editorial; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 1
DOI: 10.1021/cm500005d
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“Self-limiting oxidation in small-diameter Si nanowires”. Khalilov U, Pourtois G, van Duin ACT, Neyts EC, Chemistry of materials 24, 2141 (2012). http://doi.org/10.1021/cm300707x
Abstract: Recently, core shell silicon nanowires (Si-NWs) have been envisaged to be used for field-effect transistors and photovoltaic applications. In spite of the constant downsizing of such devices, the formation of ultrasmall diameter core shell Si-NWs currently remains entirely unexplored. We report here on the modeling of the formation of such core shell Si-NWs using a dry thermal oxidation of 2 nm diameter (100) Si nanowires at 300 and 1273 K, by means of reactive molecular dynamics simulations using the ReaxFF potential. Two different oxidation mechanisms are discussed, namely a self-limiting process that occurs at low temperature (300 K), resulting in a Si core I ultrathin SiO2 silica shell nanowire, and a complete oxidation process that takes place at a higher temperature (1273 K), resulting in the formation of an ultrathin SiO2 silica nanowire. The oxidation kinetics of both cases and the resulting structures are analyzed in detail. Our results demonstrate that precise control over the Si-core radius of such NWs and the SiOx (x <= 2.0) oxide shell is possible by controlling the growth temperature used during the oxidation process.
Keywords: A1 Journal article; Plasma Lab for Applications in Sustainability and Medicine – Antwerp (PLASMANT)
Impact Factor: 9.466
Times cited: 45
DOI: 10.1021/cm300707x
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“Structural and magnetotransport transitions in the electron-doped Pr1-xSrxMnO3(0.85\leq x\leq1) manganites”. Hervieu M, Martin C, Maignan A, Van Tendeloo G, Jirak Z, Hejtmanek J, Barnabe A, Thopart D, Raveau B, Chemistry and materials 12, 1456 (2000). http://doi.org/10.1021/cm000016o
Abstract: The exploration of the Mn4+-rich side of the Pr1-xSrxMnO3 system has allowed the extension of the domain of the cubic perovskite, by using a two-step process, combining synthesis under Ar flow at high temperature and O-2 pressure annealing at lower temperature. We show that these Pr-doped cubic perovskites exhibit a coupled structural (cubic-tetragonal) and magnetic (para-antiferro) transition connected with a resistivity jump at the same temperature. The strong interplay between lattice, charges, and spins for these oxides results from the appearance at low temperature of the distorted C-type antiferromagnetic structure. The Pr1-xSrxMnO3 magnetic phase diagram shows, for 0.9 less than or equal to x less than or equal to 1 (i.e., on the Mn4+-rich side), the existence at low temperature of C- and G-type antiferromagnetism. The absence of ferromagnetic-antiferromagnetic competition explains that magnetoresistante properties are not observed in this system, in contrast to Mn4+-rich Ln(1-x)Ca(x)MnO(3) systems.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 24
DOI: 10.1021/cm000016o
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“Structural evolution of the BiFeO3-LaFeO3 system”. Rusakov D, Abakumov AM, Yamaura K, Belik AA, Van Tendeloo G, Takayama-Muromachi E, Chemistry of materials 23, 285 (2011). http://doi.org/10.1021/cm1030975
Abstract: The (1 − x)BiFeO3−xLaFeO3 system has been investigated and characterized by room-temperature and high-temperature laboratory and synchrotron powder X-ray diffraction, electron diffraction, high-resolution transmission electron microscopy, differential scanning calorimetry, and magnetization measurements. At room temperature, the ferroelectric R3c phase is observed for 0.0 ≤ x ≤ 0.10. The PbZrO3-related √2ap × 2√2ap × 4ap superstructure (where ap is the parameter of the cubic perovskite subcell) is observed for Bi0.82La0.18FeO3, while an incommensurately modulated phase is formed for 0.19 ≤ x ≤ 0.30 with the √2ap × 2ap × √2ap basic unit cell. The GdFeO3-type phase with space group Pnma (√2ap × 2ap × √2ap) is stable at 0.50 ≤ x ≤ 1. Bi0.82La0.18FeO3 has no detectable homogeneity range (space group Pnam, a = 5.6004(1) Å, b = 11.2493(3) Å, c = 15.6179(3) Å). The incommensurately modulated Bi0.75La0.25FeO3 structure was solved from synchrotron X-ray powder diffraction data (Imma(00γ)s00 superspace group, a = 5.5956(1) Å, b = 7.8171(1) Å, c = 5.62055(8) Å, q = 0.4855(4)c*, RP = 0.023, RwP = 0.033). In this structure, cooperative displacements of the Bi and O atoms occur, which order within the (AO) (where A = Bi, La) layers, resulting in an antipolar structure. Local fluctuations of the intralayer antipolar ordering are compensated by an interaction with the neighboring (AO) layers. A coupling of the antipolar displacements with the cooperative tilting distortion of the perovskite octahedral framework is proposed as the origin of the incommensurability. All the phases transform to the GdFeO3-type structure at high temperatures. Bi0.82La0.18FeO3 shows an intermediate PbZrO3-type phase with √2ap × 2√2ap × 2ap (space group Pbam; a = 5.6154(2) Å, b = 11.2710(4) Å, and c = 7.8248(2) Å at 570 K). The compounds in the compositional range of 0.18 ≤ x ≤ 0.95 are canted antiferromagnets.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 133
DOI: 10.1021/cm1030975
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“Structure and microstructure of epitaxial Sr4Fe6O13-\delta films on SrTiO3”. Rossell MD, Abakumov AM, Van Tendeloo G, Pardo JA, Santiso J, Chemistry and materials 16, 2578 (2004). http://doi.org/10.1021/cm0498234
Abstract: The crystal structure and the microstructure of epitaxial Sr4Fe6O13+/-delta thin films grown on a single-crystal SrTiO3 substrate by PLD have been investigated. A combination of electron diffraction and high-resolution microscopy allows us to refine the structure and to identify an incommensurate modulation in the Sr4Fe6O13+/-delta films. The incommensurate structure (q = alphaa(m)* approximate to 0.39alpha(m)*, superspace group Xmmm(alpha00)0s0) can be interpreted as an oxygen-deficient modification in the Fe2O2.5 double layers. Moreover, it is shown that the experimentally determined a component of the modulation can be used consistently to estimate the local oxygen content in the Sr4Fe6O13+/-delta films. The compound composition can therefore be described as Sr4Fe6O12+2alpha and the value alpha = 0.39 corresponds to a Sr4Fe6O12.78 composition. The misfit stress along the Sr4Fe6O13+/-delta/SrTiO3 interface is accommodated via both elastic deformation and inelastic mechanisms (misfit dislocations and 90degrees rotation twins). The present results also suggest the existence of SrFeO3 perovskite in the Sr4Fe6O13+/-delta films.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 26
DOI: 10.1021/cm0498234
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“Superspace description, crystal structures, and electric conductiof the Ba4In6-xMgxO13-x/2 solid solutions”. Abakumov AM, Rossell MD, Gutnikova OY, Drozhzhin OA, Leonova LS, Dobrovolsky YA, Istomin SY, Van Tendeloo G, Antipov EV, Chemistry of materials 20, 4457 (2008). http://doi.org/10.1021/cm8004216
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 15
DOI: 10.1021/cm8004216
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“Synthesis and properties of charge-ordered thallium halide perovskites, CsTl0.5+Tl0.53+X3 (X = F or Cl) : theoretical precursors for superconductivity?”. Retuerto M, Emge T, Hadermann J, Stephens PW, Li MR, Yin ZP, Croft M, Ignatov A, Zhang SJ, Yuan Z, Jin C, Simonson JW, Aronson MC, Pan A, Basov DN, Kotliar G, Greenblatt M;, Chemistry of materials 25, 4071 (2013). http://doi.org/10.1021/cm402423x
Abstract: Recently, CsTlCl3 and CsTlF3 perovskites were theoretically predicted to be potential superconductors if they were optimally doped. The syntheses of these two compounds together with a complete characterization of the samples are reported. CsTlCl3 was obtained as orange crystals in two different polymorphs: a tetragonal phase (I4/m) and a cubic phase (Fm (3) over barm). CsTlF3 was formed as a light brown powder, and also as a double cubic perovskite (Fm (3) over barm). In all three CsTlX3 phases, Tl+ and Tl3+ were located in two different crystallographic positions that accommodate their different bond lengths. In CsTlCl3, some Tl vacancies were found in the Tl+ position. The charge ordering between Tl+ and Tl3+ was confirmed by X-ray absorption and Raman spectroscopy. The Raman spectroscopy of CsTlCl3 at high pressure (58 GPa) did not indicate any phase transition to a possible single Tl2+ state. However, the highly insulating material became less resistive with an increasing high pressure, while it underwent a change in its optical properties, from transparent to deeply opaque red, indicative of a decrease in the magnitude of the band gap. The theoretical design and experimental validation of the existence of CsTlF3 and CsTlCl3 cubic perovskites are the necessary first steps in confirming the theoretical prediction of superconductivity in these materials.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 28
DOI: 10.1021/cm402423x
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“Synthesis and structure of Bi14O20(SO4), a new bismuth oxide sulfate”. Francesconi MG, Kirbyshire AL, Greaves C, Richard O, Van Tendeloo G, Chem. mater. 10, 626 (1998). http://doi.org/10.1021/cm9706255
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 30
DOI: 10.1021/cm9706255
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“Synthesis, crystal structure, and magnetic properties of Srl.31Co0.63Mn0.3703: a reivative of the incommensurate composite hexagonal perovskite structure”. Mandal TK, Abakumov AM, Hadermann J, Van Tendeloo G, Croft M, Greenblatt M, Chemistry of materials 19, 6158 (2007). http://doi.org/10.1021/cm071840g
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 5
DOI: 10.1021/cm071840g
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“_Fe2O3 nanoparticles with mesoporous MCM-48 silica: in situ formation and characterisation”. Fröba M, Köhn R, Bouffaud G, Richard O, Van Tendeloo G, Chemistry of materials 11, 2858 (1999). http://doi.org/10.1021/cm991048i
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 202
DOI: 10.1021/cm991048i
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“Li2Cu2O(SO4)2: a possible electrode for sustainable Li-based batteries showing a 4.7 V redox activity vs Li+/Li0”. Sun M, Rousse G, Abakumov AM, Saubanere M, Doublet M-L, Rodriguez-Carvajal J, Van Tendeloo G, Tarascon J-M, Chemistry of materials 27, 3077 (2015). http://doi.org/10.1021/acs.chemmater.5b00588
Abstract: Li-ion batteries rely on the use of insertion positive electrodes with performances scaling with the redox potential of the 31) metals accompanying Liuptake/removal. Although not commonly studied, the Cu2+/Cu3+ redox potential has been predicted from theoretical calculations to possibly offer a high operating voltage redox couple. We herein report the synthesis and crystal structure of a hitherto-unknown oxysulfate phase, Li2Cu2O(SO4)(2), which contains infinite edgesharing CuO4 chains and presents attractive electrochemical redox activity with respect to Li+/Li, namely amphoteric characteristics. Li2Cu2O(SO4)(2) shows redox activity at 4.7 V vs Li+/Li corresponding to the oxidation of Cu2+ to Cu3+ enlisting ligand holes and associated with the reversible uptake-removal of 0.3 Li. Upon reduction, this compound reversibly uptakes similar to 2 Li at an average potential of about 2.5 V vs Li+/Li, associated with the Cu2+/Cu+ redox couple. The mechanism of the reactivity upon reduction is discussed in detail, with particular attention to the occasional appearance of an oscillation wave in the discharge profile. Our work demonstrates that Cu-based compounds can indeed be fertile scientific ground in the search for new high-energy-density electrodes.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 20
DOI: 10.1021/acs.chemmater.5b00588
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“Sn2-2xSbxFexO4 solid solutions as possible inert anode materials in aluminum electrolysis”. Govorov VA, Abakumov AM, Rozova MG, Borzenko AG, Vassiliev SY, Mazin VM, Afanasov MI, Fabritchnyi PB, Tsirlina GA, Antipov EV, Morozova EN, Gippius AA, Ivanov VV, Van Tendeloo G, Chemistry of materials 17, 3004 (2005). http://doi.org/10.1021/cm048145i
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 11
DOI: 10.1021/cm048145i
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“Sr3Fe5/4Mo3/4O6.9, an n = 2 Ruddlesden-Popper phase: synthesis and properties”. Whaley LW, Lobanov MV, Sheptyakov D, Croft M, Ramanujachary KV, Lofland S, Stephens PW, Her JH, Van Tendeloo G, Rossell M, Greenblatt M;, Chemistry of materials 18, 3448 (2006). http://doi.org/10.1021/cm060482z
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 15
DOI: 10.1021/cm060482z
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“Topotactic transformation of the cationic conductor Li4Mo5O17 into a rock salt type oxide Li12Mo5O17”. Pop N, Pralong V, Caignaert V, Colin JF, Malo S, Van Tendeloo G, Raveau B, Chemistry of materials 21, 3242 (2009). http://doi.org/10.1021/cm900767m
Abstract: Intercalation of lithium in the ribbon structure Li4Mo5O17 has been achieved, using both electrochemistry and soft chemistry. The ab initio structure determination of the ¡°Mo−O¡± framework of Li12Mo5O17 shows that the [Mo5O17]¡Þ ribbons keep the same arrangement of edge sharing MoO6 octahedra and the same orientation as in the parent structure but that a topotactic antidistortion of the ribbons appears, as a result of the larger size of Mo4+ in ¡°Li12¡± compared to Mo6+ in ¡°Li4¡±. On the basis of bond valence calculations, it is observed that 12 octahedral sites are available for Li+ in the new structure so that an ordered hypothetical rock salt type structure can be proposed for Li12Mo5O17. After the first Li insertion, a stable reversible capacity of 100 mA¡¤h/g is maintained after 20 cycles. A complete structural reversibility leading back to the ribbon type Li4Mo5O17 structure is obtained using a very low rate of C/100. The exploration of the Li mobility in those oxides shows that Li4Mo5O17 is a cationic conductor with ¦Ò = 10−3.5 S/cm at 500 ¡ãC and Ea = 0.35 eV.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 18
DOI: 10.1021/cm900767m
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“Transmission electron microscopic study of the defect structure in Sr4Fe6O12+\delta compounds with variable oxygen content”. Rossell MD, Abakumov AM, Van Tendeloo G, Lomakov MV, Istomin SY, Antipov EV, Chemistry and materials 17, 4717 (2005). http://doi.org/10.1021/cm050777x
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 17
DOI: 10.1021/cm050777x
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“Uniform patterns of Fe-vacancy ordering in the Kx(Fe,Co)2-ySe2 superconductors”. Kazakov SM, Abakumov AM, Perz-Mato JM, Ovchinnikov AV, Roslova MV, Boltalin AI, Morozov IV, Antipov EV, Van Tendeloo G, Chemistry of materials 23, 4311 (2011). http://doi.org/10.1021/cm201203h
Abstract: The Fe-vacancy ordering patterns in the superconducting KxFe2ySe2 and nonsuperconducting Kx(Fe,Co)2ySe2 samples have been investigated by electron diffraction and high angle annular dark field scanning transmission electron microscopy. The Fe-vacancy ordering occurs in the ab plane of the parent ThCr2Si2-type structure, demonstrating two types of patterns. Superstructure I retains the tetragonal symmetry and can be described with the aI = bI = as√5 (as is the unit cell parameter of the parent ThCr2Si2-type structure) supercell and I4/m space group. Superstructure II reduces the symmetry to orthorhombic with the aII = as√2, bII = 2as√2 supercell and the Ibam space group. This type of superstructure is observed for the first time in KxFe2ySe2. The Fe-vacancy ordering is inhomogeneous: the disordered areas interleave with the superstructures I and II in the same crystallite. The observed superstructures represent the compositionally dependent uniform ordering patterns of two species (the Fe atoms and vacancies) on a square lattice. More complex uniform ordered configurations, including compositional stripes, can be predicted for different chemical compositions of the KxFe2ySe2 (0 < y < 0.5) solid solutions.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 20
DOI: 10.1021/cm201203h
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