“_BiMnFe2O6, a polysynthetically twinned hcp MO structure”. Yang T, Abakumov AM, Hadermann J, Van Tendeloo G, Nowik I, Stephens PW, Hamberger J, Tsirlin AA, Ramanujachary KV, Lofland S, Croft M, Ignatov A, Sun J, Greenblatt M, Chemical science 1, 751 (2010). http://doi.org/10.1039/c0sc00348d
Abstract: The most efficient use of spatial volume and the lowest potential energies in the metal oxide structures are based on cubic close packing (ccp) or hexagonal close packing (hcp) of anions with cations occupying the interstices. A promising way to tune the composition of close packed oxides and design new compounds is related to fragmenting the parent structure into modules by periodically spaced planar interfaces, such as twin planes at the unit cell scale. The unique crystal chemistry properties of cations with a lone electron pair, such as Bi3+ or Pb2+, when located at interfaces, enables them to act as chemical scissors, to help relieve configurational strain. With this approach, we synthesized a new oxide, BiMnFe2O6, where fragments of the hypothetical hcp oxygen-based MO structure (the NiAs structure type), for the first time, serve as the building modules in a complex transition metal oxide. Mn3+ and Fe3+ ions are randomly distributed in two crystallographically independent sites (M1 and M2). The structure consists of quasi two-dimensional blocks of the 2H hexagonal close packed MO structure cut along the (114) crystal plane of the hcp lattice and stacked along the c axis. The blocks are related by a mirror operation that allows BiMnFe2O6 to be considered as a polysynthetically twinned 2H hcp MO structure. The transition to an AFM state with an incommensurate spin configuration at [similar] 212 K is established by 57Fe Mössbauer spectroscopy, magnetic susceptibility, specific heat and low temperature powder neutron diffraction.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 8.668
Times cited: 12
DOI: 10.1039/c0sc00348d
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“MnFe0.5Ru0.5O3 : an above-room-temperature antiferromagnetic semiconductor”. Tan X, McCabe EE, Orlandi F, Manuel P, Batuk M, Hadermann J, Deng Z, Jin C, Nowik I, Herber R, Segre CU, Liu S, Croft M, Kang C-J, Lapidus S, Frank CE, Padmanabhan H, Gopalan V, Wu M, Li M-R, Kotliar G, Walker D, Greenblatt M, Journal of materials chemistry C : materials for optical and electronic devices 7, 509 (2019). http://doi.org/10.1039/C8TC05059G
Abstract: A transition-metal-only MnFe0.5Ru0.5O3 polycrystalline oxide was prepared by a reaction of starting materials MnO, MnO2, Fe2O3, RuO2 at 6 GPa and 1873 K for 30 minutes. A combination of X-ray and neutron powder diffraction refinements indicated that MnFe0.5Ru0.5O3 adopts the corundum (alpha-Fe2O3) structure type with space group R (3) over barc, in which all metal ions are disordered. The centrosymmetric nature of the MnFe0.5Ru0.5O3 structure is corroborated by transmission electron microscopy, lack of optical second harmonic generation, X-ray absorption near edge spectroscopy, and Mossbauer spectroscopy. X-ray absorption near edge spectroscopy of MnFe0.5Ru0.5O3 showed the oxidation states of Mn, Fe, and Ru to be 2+/3+, 3+, and similar to 4+, respectively. Resistivity measurements revealed that MnFe0.5Ru0.5O3 is a semiconductor. Magnetic measurements and magnetic structure refinements indicated that MnFe0.5Ru0.5O3 orders antiferromagnetically around 400 K, with magnetic moments slightly canted away from the c axis. Fe-57 Mossbauer confirmed the magnetic ordering and Fe3+ (S = 5/2) magnetic hyperfine splitting. First principles calculations are provided to understand the electronic structure more thoroughly. A comparison of synthesis and properties of MnFe0.5Ru0.5O3 and related corundum Mn2BB'O-6 derivatives is discussed.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 5.256
Times cited: 1
DOI: 10.1039/C8TC05059G
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“La1.5Sr0.5NiMn0.5Ru0.5O6 double perovskite with enhanced ORR/OER bifunctional catalytic activity”. Retuerto M, Calle-Vallejo F, Pascual L, Lumbeeck G, Fernandez-Diaz MT, Croft M, Gopalakrishnan J, Pena MA, Hadermann J, Greenblatt M, Rojas S, ACS applied materials and interfaces 11, 21454 (2019). http://doi.org/10.1021/ACSAMI.9B02077
Abstract: Perovskites (ABO(3)) with transition metals in active B sites are considered alternative catalysts for the water oxidation to oxygen through the oxygen evolution reaction (OER) and for the oxygen reduction through the oxygen reduction reaction (ORR) back to water. We have synthesized a double perovskite (A(2)BB'O-6) with different cations in A, B, and B' sites, namely, ((La15Sr0.5)-Sr-.)(A)(Ni0.5Mn0.5)(B)(Ni0.5Ru0.5)(B)O-6 (LSNMR), which displays an outstanding OER/ORR bifunctional performance. The composition and structure of the oxide has been determined by powder X-ray diffraction, powder neutron diffraction, and transmission electron microscopy to be monoclinic with the space group P2(1)/n and with cationic ordering between the ions in the B and B' sites. X-ray absorption near-edge spectroscopy suggests that LSNMR presents a configuration of similar to Ni2+, similar to Mn4+, and similar to Ru5+. This bifunctional catalyst is endowed with high ORR and OER activities in alkaline media, with a remarkable bifunctional index value of similar to 0.83 V (the difference between the potentials measured at -1 mA cm(-2) for the ORR and +10 mA cm(-2) for the OER). The ORR onset potential (E-onset) of 0.94 V is among the best reported to date in alkaline media for ORR-active perovskites. The ORR mass activity of LSNMR is 1.1 A g(-1) at 0.9 V and 7.3 A g(-1) at 0.8 V. Furthermore, LSNMR is stable in a wide potential window down to 0.05 V. The OER potential to achieve a current density of 10 mA cm(-2) is 1.66 V. Density functional theory calculations demonstrate that the high ORR/OER activity of LSNMR is related to the presence of active Mn sites for the ORR- and Ru-active sites for the OER by virtue of the high symmetry of the respective reaction steps on those sites. In addition, the material is stable to ORR cycling and also considerably stable to OER cycling.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Impact Factor: 7.504
Times cited: 12
DOI: 10.1021/ACSAMI.9B02077
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“Synthesis and charactreization of the new Ln(2)FeMoO(7) (Ln = Y, Dy, Ho) compounds”. Veith GM, Lobanov MV, Emge TJ, Greenblatt M, Croft M, Stowasser F, Hadermann J, Van Tendeloo G, Journal of materials chemistry 14, 1623 (2004). http://doi.org/10.1039/b315028c
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Times cited: 17
DOI: 10.1039/b315028c
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“Synthesis, cation ordering, and magnetic properties of the (Sb1-xPbx)2(Mn1-ySby)O4 solid solutions with the Sb2MnO4-type structure”. Abakumov AM, Rozova MG, Antipov EV, Hadermann J, Van Tendeloo G, Lobanov MV, Greenblatt M, Croft M, Tsiper EV, Llobet A, Lokshin KA, Zhao Y, Chemistry of materials 17, 1123 (2005). http://doi.org/10.1021/cm048791h
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 16
DOI: 10.1021/cm048791h
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“Crystal structure and properties of Ru-stoichiometric LaSrMnRuO6”. Bune RO, Lobanov MV, Popov G, Greenblatt M, Botez CE, Stephens PW, Croft M, Hadermann J, Van Tendeloo G, Chemistry of materials 18, 2611 (2006). http://doi.org/10.1021/cm052371q
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 17
DOI: 10.1021/cm052371q
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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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“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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“La2MnVO6 double perovskite: a structural, magnetic and X-ray absorption investigation”. Mandal TK, Croft M, Hadermann J, Van Tendeloo G, Stephens PW, Greenblatt M, Journal of materials chemistry 19, 4382 (2009). http://doi.org/10.1039/b823513a
Abstract: The synthesis, electron diffraction (ED), synchrotron X-ray and neutron structure, X-ray absorption spectroscopy (XAS) and magnetic property studies of La2MnVO6 double perovskite are described. Analysis of the synchrotron powder X-ray diffraction data for La2MnVO6 indicates a disordered arrangement of Mn and V at the B-site of the perovskite structure. Absence of super-lattice reflections in the ED patterns for La2MnVO6 supports the disordered cation arrangement. Room temperature time-of-flight (TOF) neutron powder diffraction (NPD) data show no evidence of cation ordering, in corroboration with the ED and synchrotron studies (orthorhombic Pnma, a = 5.6097(3), b = 7.8837(5) and c = 5.5668(3) ; 295 K, NPD). A comparison of XAS analyses of La2TVO6 with T = Ni and Co shows T2+ formal oxidation state while the T = Mn material evidences a Mn3+ admixture into a dominantly Mn2+ ground state. V-K edge measurements manifest a mirror image behavior with a V4+ state for T = Ni and Co with a V3+ admixture arising in the T = Mn material. The magnetic susceptibility data for La2MnVO6 show ferromagnetic correlations; the observed effective moment, µeff (5.72 µB) is much smaller than the calculated moment (6.16 µB) based on the spin-only formula for Mn2+ (d5, HS) /V4+ (d1), supportive of the partly oxidized Mn and reduced V scenario (Mn3+/V3+).
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Times cited: 10
DOI: 10.1039/b823513a
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“Synthesis and structure determination of ferromagnetic semiconductors LaAMnSnO6(A = Sr, Ba)”. Yang T, Perkisas T, Hadermann J, Croft M, Ignatov A, Van Tendeloo G, Greenblatt M, Journal of materials chemistry 21, 199 (2011). http://doi.org/10.1039/c0jm02614j
Abstract: LaAMnSnO(6) (A = Sr, Ba) have been synthesized by high temperature solid-state reactions under dynamic 1% H(2)/Ar flow. Rietveld refinements on room temperature powder X-ray diffraction data indicate that LaSrMnSnO(6) crystallizes in the GdFeO(3)-structure, with space group Pnma and, combined with transmission electron microscopy, LaBaMnSnO(6) in Imma. Both space groups are common in disordered double-perovskites. The Mn(3+) and Sn(4+) ions whose valence states were confirmed by X-ray absorption spectroscopy, are completely disordered over the B-sites and the BO(6) octahedra are slightly distorted. LaAMnSnO(6) are ferromagnetic semiconductors with a T(C) = 83 K for the Sr- and 66 K for the Ba-compound. The title compounds, together with the previously reported LaCaMnSnO(6) provide an interesting example of progression from Pnma to Imma as the tolerance factor increases. An analysis of the relationship between space group and tolerance factor for the series LaAMnMO(6) (A = Ca, Sr, Ba; M = Sn, Ru) provides a better understanding of the symmetry determination for double perovskites.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Times cited: 3
DOI: 10.1039/c0jm02614j
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“Short-range layered A-site ordering in double perovskites NaLaBB'O6 (B = Mn, Fe, B' = Nb, Ta)”. Dachraoui W, Yang T, Liu C, Ling G, Hadermann J, Van Tendeloo G, Llobet A, Greenblatt M, Chemistry of materials 23, 2398 (2011). http://doi.org/10.1021/cm200226u
Abstract: The new compounds NaLaFeTaO6, NaLaFeNbO6, NaLaMnTaO6, and NaLaMnNbO6 have been synthesized and characterized with a combination of transmission electron microscopy, X-ray powder diffraction (XRPD), neutron powder diffraction (NPD), and magnetization measurements. Through electron microscopy study, a local layered order of the A-cations has been detected without the typical occurrence of rock salt order at the B-cation site. Satellite reflections in the electron diffraction related to the local layered order are not visible on the XRPD or NPD patterns. The occurrence of local layered order is supported by pair distribution function analysis, which also reveals the presence of uncorrelated displacements of the Nb and Ta cations. The octahedra are tilted according to the system a−b+a−, and the coordinates were refined from XRPD and NPD with a disordered cation distribution in the space group Pnma. The magnetic exchange interactions in NaLaFeTaO6 and NaLaFeNbO6 are antiferromagnetic, while they are ferromagnetic in NaLaMnTaO6 and NaLaMnNbO6. Long-range magnetic ordering is not observed down to 4 K for any of the compositions.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 14
DOI: 10.1021/cm200226u
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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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“Mn2FeWO6 : a new Ni3TeO6-type polar and magnetic oxide”. Li MR, Croft M, Stephens PW, Ye M, Vanderbilt D, Retuerto M, Deng Z, Grams CP, Hemberger J, Hadermann J, Li WM, Jin CQ, Saouma FO, Jang JI, Akamatsu H, Gopalan V, Walker D, Greenblatt M;, Advanced materials 27, 2177 (2015). http://doi.org/10.1002/adma.201405244
Abstract: Mn22+Fe2+W6+O6, a new polar magnetic phase, adopts the corundum-derived Ni3TeO6-type structure with large spontaneous polarization (P-S) of 67.8 mu C cm-2, complex antiferromagnetic order below approximate to 75 K, and field-induced first-order transition to a ferrimagnetic phase below approximate to 30 K. First-principles calculations predict a ferrimagnetic (udu) ground state, optimal switching path along the c-axis, and transition to a lower energy udu-udd magnetic double cell.
Keywords: A1 Journal article; Engineering sciences. Technology; Electron microscopy for materials research (EMAT)
Impact Factor: 19.791
Times cited: 32
DOI: 10.1002/adma.201405244
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“Tetragonal Cs1.17In0.81Cl3 : a charge-ordered indium halide perovskite derivative”. Tan X, Stephens PW, Hendrickx M, Hadermann J, Segre CU, Croft M, Kang C-J, Deng Z, Lapidus SH, Kim SW, Jin C, Kotliar G, Greenblatt M, Chemistry of materials 31, 1981 (2019). http://doi.org/10.1021/ACS.CHEMMATER.8B04771
Abstract: Polycrystalline samples of Cs1.17In0.81Cl3 were prepared by annealing a mixture of CsCl, InCl, and InCl3, stoichiometric for the targeted CsInCl3. Synchrotron powder X-ray diffraction refinement and chemical analysis by energy dispersive X-ray indicated that Cs1.17In0.81Cl3, a tetragonal distorted perovskite derivative (I4/m), is the thermodynamically stable product. The refined unit cell parameters and space group were confirmed by electron diffraction. In the tetragonal structure, In+ and In3+ are located in four different crystallographic sites, consistent with their corresponding bond lengths. In1, In2, and In3 are octahedrally coordinated, whereas In4 is at the center of a pentagonal bipyramid of Cl because of the noncooperative octahedral tilting of In4Cl6. The charged-ordered In+ and In3+ were also confirmed by X-ray absorption and Raman spectroscopy. Cs1.17In0.81Cl3 is the first example of an inorganic halide double perovskite derivative with charged-ordered In+ and In3+. Band structure and optical conductivity calculations were carried out with both generalized gradient approximation (GGA) and modified Becke-Johnson (mBJ) approach; the GGA calculations estimated the band gap and optical band gap to be 2.27 eV and 2.4 eV, respectively. The large and indirect band gap suggests that Cs1.17In0.81Cl3 is not a good candidate for photovoltaic application.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
Times cited: 6
DOI: 10.1021/ACS.CHEMMATER.8B04771
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“Antiferromagnetic order breaks inversion symmetry in a metallic double perovskite, Pb₂NiOsO₆”. Feng HL, Kang C-J, Manuel P, Orlandi F, Su Y, Chen J, Tsujimoto Y, Hadermann J, Kotliar G, Yamaura K, McCabe EE, Greenblatt M, Chemistry Of Materials 33, 4188 (2021). http://doi.org/10.1021/ACS.CHEMMATER.1C01032
Abstract: A polycrystalline sample of Pb2NiOsO6 was synthesized under high-pressure (6 GPa) and high-temperature (1575 K) conditions. Pb2NiOsO6 crystallizes in a monoclinic double perovskite structure with a centrosymmetric space group P2(1)/n at room temperature. Pb2NiOsO6 is metallic down to 2 K and shows a single antiferromagnetic (AFM) transition at T-N = 58 K. Pb2NiOsO6 is a new example of a metallic and AFM oxide with three-dimensional connectivity. Neutron powder diffraction and first-principles calculation studies indicate that both Ni and Os moments are ordered below T-N and the AFM magnetic order breaks inversion symmetry. This loss of inversion symmetry driven by AFM order is unusual in metallic systems, and the 3d-Sd double-perovskite oxides represent a new class of noncentrosymmetric AFM metallic oxides.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 9.466
DOI: 10.1021/ACS.CHEMMATER.1C01032
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“Crystal structure and magnetic properties of the Cr-doped spiral antiferromagnet BiMnFe2O6”. Batuk D, de Dobbelaere C, Tsirlin AA, Abakumov AM, Hardy A, van Bael MK, Greenblatt M, Hadermann J, Materials research bulletin 48, 2993 (2013). http://doi.org/10.1016/j.materresbull.2013.04.038
Abstract: We report the Cr3+ for Mn3+ substitution in the BiMnFe2O6 structure. The BiCrxMn1-xFe2O6 solid solution is obtained by the solution-gel synthesis technique for the x values up to 0.3. The crystal structure investigation using a combination of X-ray powder diffraction and transmission electron microscopy demonstrates that the compounds retain the parent BiMnFe2O6 structure (for x = 0.3, a = 5.02010(6)angstrom, b = 7.06594(7)angstrom, c = 12.6174(1)angstrom, S.G. Pbcm, R-1 = 0.036, R-p = 0.011) with only a slight decrease in the cell parameters associated with the Cr3+ for Mn3+ substitution. Magnetic susceptibility measurements suggest strong similarities in the magnetic behavior of BiCrxMn1-xFe2O6 (x = 0.2; 0.3) and parent BiMnFe2O6. Only T-N slightly decreases upon Cr doping that indicates a very subtle influence of Cr3+ cations on the magnetic properties at the available substitution rates. (C) 2013 Elsevier Ltd. All rights reserved.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 2.446
Times cited: 3
DOI: 10.1016/j.materresbull.2013.04.038
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“Magnetic and structural studies of the multifunctional material SrFe0.75Mo0.25O3-\text{\textgreek{d}}”. Retuerto M, Li MR, Go YB, Ignatov A, Croft M, Ramanujachary KV, Hadermann J, Hodges JP, Herber RH, Nowik I, Greenblatt M;, Inorganic chemistry 51, 12273 (2012). http://doi.org/10.1021/ic301550m
Abstract: SrFe0.75Mo0.25O3-delta has been recently discovered as an extremely efficient electrode for intermediate temperature solid oxide fuel cells (IT-SOFCs). We have performed structural and magnetic studies to fully characterize this multifunctional material. We have observed by powder neutron diffraction (PND) and transmission electron microscopy (TEM) that its crystal symmetry is better explained with a tetragonal symmetry (I4/mcm space group) than with the previously reported orthorhombic symmetry (Pnma space group). The temperature dependent magnetic properties indicate an exceptionally high magnetic ordering temperature (T-N similar to 750 K), well above room temperature. The ordered magnetic structure at low temperature was determined by PND to be an antiferromagnetic coupling of the Fe cations. Mossbauer spectroscopy corroborated the PND results. A detailed study, with X-ray absorption spectroscopy (XAS), in agreement with the Mossbauer results, confirmed the formal oxidation states of the cations to be mixed valence Fe3+/4+ and Mo6+.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 4.857
Times cited: 12
DOI: 10.1021/ic301550m
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“Structural requirements in lithium cobalt oxides for the catalytic oxidation of water”. Gardner GP, Go YB, Robinson DM, Smith PF, Hadermann J, Abakumov A, Greenblatt M, Dismukes GC, Angewandte Chemie: international edition in English 51, 1616 (2012). http://doi.org/10.1002/anie.201107625
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 11.994
Times cited: 119
DOI: 10.1002/anie.201107625
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“Polar and magnetic layered A-site and rock salt B-site-ordered NaLnFeWO6 (Ln = La, Nd) perovskites”. Retuerto M, Li MR, Ignatov A, Croft M, Ramanujachary KV, Chi S, Hodges JP, Dachraoui W, Hadermann J, Tran TT, Halasyamani PS, Grams CP, Hemberger J, Greenblatt M;, Inorganic chemistry 52, 12482 (2013). http://doi.org/10.1021/ic401491y
Abstract: We have expanded the double perovskite family of materials with the unusual combination of layered order in the A sublattice and rock salt order over the B sublattice to compounds NaLaFeWO6 and NaNdFeWO6. The materials have been synthesized and studied by powder X-ray diffraction, neutron diffraction, electron diffraction, magnetic measurements, X-ray absorption spectroscopy, dielectric measurements, and second harmonic generation. At room temperature, the crystal structures of both compounds can be defined in the noncentrosymmetric monoclinic P2(1) space group resulting from the combination of ordering both in the A and B sublattices, the distortion of the cell due to tilting of the octahedra, and the displacement of certain cations. The magnetic studies show that both compounds are ordered antiferromagnetically below T-N approximate to 25 K for NaLaFeWO6 and at similar to 21 K for NaNdFeWO6. The magnetic structure of NaNdFeWO6 has been solved with a propagation vector k = (1/2 0 1/2) as an antiferromagnetic arrangement of Fe and Nd moments. Although the samples are potential multiferroics, the dielectric measurements do not show a ferroelectric response.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 4.857
Times cited: 17
DOI: 10.1021/ic401491y
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“Polar and magnetic Mn2FeMO6 (M=Nb, Ta) with LiNbO3-type structure : high-pressure synthesis”. Li MR, Walker D, Retuerto M, Sarkar T, Hadermann J, Stephens PW, Croft M, Ignatov A, Grams CP, Hemberger J, Nowik I, Halasyamani PS, Tran TT, Mukherjee S, Dasgupta TS, Greenblatt M;, Angewandte Chemie: international edition in English 52, 8406 (2013). http://doi.org/10.1002/anie.201302775
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 11.994
Times cited: 53
DOI: 10.1002/anie.201302775
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“Hole doping and structural transformation in CsTl1-xHgxCl3”. Retuerto M, Yin Z, Emge TJ, Stephens PW, Li MR, Sarkar T, Croft MC, Ignatov A, Yuan Z, Zhang SJ, Jin C, Paria Sena R, Hadermann J, Kotliar G, Greenblatt M;, Inorganic chemistry 54, 1066 (2015). http://doi.org/10.1021/ic502400d
Abstract: CsTlCl3 and CsTlF3 perovskites have been theoretically predicted to be superconductors when properly hole-doped. Both compounds have been previously prepared as pure compounds: CsTlCl3 in a tetragonal (I4/m) and a cubic (Fm3̅m) perovskite polymorph and CsTlF3 as a cubic perovskite (Fm3̅m). In this work, substitution of Tl in CsTlCl3 with Hg is reported, in an attempt to hole-dope the system and induce superconductivity. The whole series CsTl1xHgxCl3 (x = 0.0, 0.1, 0.2, 0.4, 0.6, and 0.8) was prepared. CsTl0.9Hg0.1Cl3 is tetragonal as the more stable phase of CsTlCl3. However, CsTl0.8Hg0.2Cl3 is already cubic with the space group Fm3̅m and with two different positions for Tl+ and Tl3+. For x = 0.4 and 0.5, solid solutions could not be formed. For x ≥ 0.6, the samples are primitive cubic perovskites with one crystallographic position for Tl+, Tl3+, and Hg2+. All of the samples formed are insulating, and there is no signature of superconductivity. X-ray absorption spectroscopy indicates that all of the samples have a mixed-valence state of Tl+ and Tl3+. Raman spectroscopy shows the presence of the active TlClTl stretching mode over the whole series and the intensity of the TlClHg mode increases with increasing Hg content. First-principle calculations confirmed that the phases are insulators in their ground state and that Hg is not a good dopant in the search for superconductivity in this system.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 4.857
Times cited: 5
DOI: 10.1021/ic502400d
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“Giant magnetoresistance in the half-metallic double-perovskite ferrimagnet Mn2FeReO6”. Li MR, Retuerto M, Deng Z, Stephens PW, Croft M, Huang Q, Wu H, Deng X, Kotliar G, Sánchez-Benítez J, Hadermann J, Walker D, Greenblatt M;, Angewandte Chemie: international edition in English 54, 12069 (2015). http://doi.org/10.1002/anie.201506456
Abstract: The first transition-metal-only double perovskite compound, Mn2+ Fe-2(3+) Re5+ O-6, with 17 unpaired d electrons displays ferrimagnetic ordering up to 520K and a giant positive magnetoresistance of up to 220% at 5K and 8 T. These properties result from the ferrimagnetically coupled Fe and Re sublattice and are affected by a two-to-one magnetic-structure transition of the Mn sublattice when a magnetic field is applied. Theoretical calculations indicate that the half-metallic state can be mainly attributed to the spin polarization of the Fe and Re sites.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 11.994
DOI: 10.1002/anie.201506456
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“Pb2MnTeO6 double perovskite : an antipolar anti-ferromagnet”. Retuerto M, Skiadopoulou S, Li MR, Abakumov AM, Croft M, Ignatov A, Sarkar T, Abbett BM, Pokorný, J, Savinov M, Nuzhnyy D, Prokleška J, Abeykoon M, Stephens PW, Hodges JP, Vaněk P, Fennie CJ, Rabe KM, Kamba S, Greenblatt M;, Inorganic chemistry 55, 4320 (2016). http://doi.org/10.1021/acs.inorgchem.6b00054
Abstract: Pb2MnTeO6, a new double perovskite, was synthesized. Its crystal structure was determined by synchrotron X-ray and powder neutron diffraction. Pb2MnTeO6 is monoclinic (I2/m) at room temperature with a regular arrangement of all the cations in their polyhedra. However, when the temperature is lowered to similar to 120 K it undergoes a phase transition from I2/m to C2/c structure. This transition is accompanied by a displacement of the Pb atoms from the center of their polyhedra due to the 6s2 lone-pair electrons, together with a surprising off-centering of Mn2+ (d5) magnetic cations. This strong first-order phase transition is also evidenced by specific heat, dielectric, Raman, and infrared spectroscopy measurements. The magnetic characterizations indicate an anti-ferromagnetic (AFM) order below TN approximate to 20 K; analysis of powder neutron diffraction data confirms the magnetic structure with propagation vector k = (0 1 0) and collinear AFM spins. The observed jump in dielectric permittivity near similar to 150 K implies possible anti-ferroelectric behavior; however, the absence of switching suggests that Pb2MnTeO6 can only be antipolar. First-principle calculations confirmed that the crystal and magnetic structures determined are locally stable and that anti-ferroelectric switching is unlikely to be observed in Pb2MnTeO6.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 4.857
Times cited: 9
DOI: 10.1021/acs.inorgchem.6b00054
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“Ba-3(Cr0.97(1)Te0.03(1))(2)TeO9: in Search of Jahn-Teller Distorted Cr(II) Oxide”. Li M-R, Deng Z, Lapidus SH, Stephens PW, Segre CU, Croft M, Sena RP, Hadermann J, Walker D, Greenblatt M, Inorganic chemistry 55, 10135 (2016). http://doi.org/10.1021/ACS.INORGCHEM.6B01047
Abstract: A novel 6H-type hexagonal perovskite Ba-3(Cr0.97(1)Te0.03(1))(2)TeO9 was prepared at high pressure (6 GPa) and temperature (1773 K). Both transmission electron microscopy and synchrotron powder X-ray diffraction data demonstrate that Ba-3(Cr0.97(1)Te0.03(1))(2)TeO9 crystallizes in P6(3)/mmc with face-shared (Cr0.97(1)Te0.03(1))O-6 octahedral pairs interconnected with TeO6 octahedra via corner-sharing. Structure analysis shows a mixed Cr2+/Cr3+ valence state with similar to 10% Cr2+. The existence of Cr2+ in Ba-3(Cr0.10(1)2+Cr0.87(1)3+Te0.036+)(2)TeO9 is further evidenced by X-ray absorption near-edge spectroscopy. Magnetic properties measurements show a paramagnetic response down to 4 K and a small glassy-state curvature at low temperature. In this work, the octahedral Cr2+O6 component is stabilized in an oxide material for the first time; the expected Jahn-Teller distortion of high-spin (d(4)) Cr2+ is not found, which is attributed to the small proportion of Cr2+ (similar to 10%) and the face-sharing arrangement of CrO6 octahedral pairs, which structurally disfavor axial distortion.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 4.857
Times cited: 2
DOI: 10.1021/ACS.INORGCHEM.6B01047
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“Ambient and high pressure CuNiSb₂, : metal-ordered and metal-disordered NiAs-type derivative pnictides”. Skaggs CM, Kang C-J, Perez CJ, Hadermann J, Emge TJ, Frank CE, Pak C, Lapidus SH, Walker D, Kotliar G, Kauzlarich SM, Tan X, Greenblatt M, Inorganic Chemistry 59, 14058 (2020). http://doi.org/10.1021/ACS.INORGCHEM.0C01848
Abstract: The mineral Zlatogorite, CuNiSb2, was synthesized in the laboratory for the first time by annealing elements at ambient pressure (CuNiSb2-AP). Rietveld refinement of synchrotron powder X-ray diffraction data indicates that CuNiSb2-AP crystallizes in the NiAs-derived structure (P (3) over bar m1, #164) with Cu and Ni ordering. The structure consists of alternate NiSb6 and CuSb6 octahedral layers via face-sharing. The formation of such structure instead of metal disordered NiAs-type structure (P6(3)/mmc, #194) is validated by the lower energy of the ordered phase by first-principle calculations. Interatomic crystal orbital Hamilton population, electron localization function, and charge density analysis reveal strong Ni-Sb, Cu-Sb, and Cu-Ni bonding and long weak Sb-Sb interactions in CuNiSb2-AP. The magnetic measurement indicates that CuNiSb2-AP is Pauli paramagnetic. First-principle calculations and experimental electrical resistivity measurements reveal that CuNiSb2-AP is a metal. The low Seebeck coefficient and large thermal conductivity suggest that CuNiSb2 is not a potential thermoelectric material. Single crystals were grown by chemical vapor transport. The high pressure sample (CuNiSb2-8 GPa) was prepared by pressing CuNiSb2-AP at 700 degrees C and 8 GPa. However, the structures of single crystal and CuNiSb2-8 GPa are best fit with a disordered metal structure in the P (3) over bar m1 space group, corroborated by transmission electron microscopy.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 4.6
DOI: 10.1021/ACS.INORGCHEM.0C01848
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“Spiral ground state against ferroelectricity in the frustrated magnet BiMnFe2O6”. Abakumov AM, Tsirlin AA, Perez-Mato JM, Petřiček V, Rosner H, Yang T, Greenblatt M, Physical review : B : condensed matter and materials physics 83, 214402 (2011). http://doi.org/10.1103/PhysRevB.83.214402
Abstract: The spiral magnetic structure and underlying spin lattice of BiMnFe2O6 are investigated by low-temperature neutron powder diffraction and density functional theory band structure calculations. In spite of the random distribution of the Mn3+ and Fe3+ cations, this centrosymmetric compound undergoes a transition into an incommensurate antiferromagnetically ordered state below TN≃220 K. The magnetic structure is characterized by the propagation vector k=[0,β,0] with β≃0.14 and the P221211′(0β0)0s0s magnetic superspace symmetry. It comprises antiferromagnetic helixes propagating along the b axis. The magnetic moments lie in the ac plane and rotate about π(1+β)≃204.8-deg angle between the adjacent magnetic atoms along b. The spiral magnetic structure arises from the peculiar frustrated arrangement of exchange couplings in the ab plane. The antiferromagnetic coupling along the c axis cancels the possible electric polarization and prevents ferroelectricity in BiMnFe2O6.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 3.836
Times cited: 12
DOI: 10.1103/PhysRevB.83.214402
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“Bulk magnetic order in a two-dimensional Ni1+/Ni2+ (d9/d8) nickelate, isoelectronic with superconducting cuprates”. Poltavets VV, Lokshin KA, Nevidomskyy AH, Croft M, Tyson TA, Hadermann J, Van Tendeloo G, Egami T, Kotliar G, ApRoberts-Warren N, Dioguardi AP, Curro NJ, Greenblatt M;, Physical review letters 104, 206403 (2010). http://doi.org/10.1103/PhysRevLett.104.206403
Abstract: The Ni(1+)/Ni(2+) states of nickelates have the identical (3d(9)/3d(8)) electronic configuration as Cu(2+)/Cu(3+) in the high temperature superconducting cuprates, and are expected to show interesting properties. An intriguing question is whether mimicking the electronic and structural features of cuprates would also result in superconductivity in nickelates. Here we report experimental evidence for a bulklike magnetic transition in La(4)Ni(3)O(8) at 105 K. Density functional theory calculations relate the transition to a spin density wave nesting instability of the Fermi surface.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 8.462
Times cited: 35
DOI: 10.1103/PhysRevLett.104.206403
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“Universal a-cation splitting in LiNbO₃-type structure driven by intrapositional multivalent coupling”. Han Y, Zeng Y, Hendrickx M, Hadermann J, Stephens PW, Zhu C, Grams CP, Hemberger J, Frank C, Li S, Wu MX, Retuerto M, Croft M, Walker D, Yao D-X, Greenblatt M, Li M-R, Journal Of The American Chemical Society 142, 7168 (2020). http://doi.org/10.1021/JACS.0C01814
Abstract: Understanding the electric dipole switching in multiferroic materials requires deep insight of the atomic-scale local structure evolution to reveal the ferroelectric mechanism, which remains unclear and lacks a solid experimental indicator in high-pressure prepared LiNbO3-type polar magnets. Here, we report the discovery of Zn-ion splitting in LiNbO3-type Zn2FeNbO6 established by multiple diffraction techniques. The coexistence of a high-temperature paraelectric-like phase in the polar Zn2FeNbO6 lattice motivated us to revisit other high-pressure prepared LiNbO3-type A(2)BB'O-6 compounds. The A-site atomic splitting (similar to 1.0-1.2 angstrom between the split-atom pair) in B/B'-mixed Zn2FeTaO6 and O/N-mixed ZnTaO2N is verified by both powder X-ray diffraction structural refinements and high angle annular dark field scanning transmission electron microscopy images, but is absent in single-B-site ZnSnO3. Theoretical calculations are in good agreement with experimental results and suggest that this kind of A-site splitting also exists in the B-site mixed Mn-analogues, Mn2FeMO6 (M = Nb, Ta) and anion-mixed MnTaO2N, where the smaller A-site splitting (similar to 0.2 angstrom atomic displacement) is attributed to magnetic interactions and bonding between A and B cations. These findings reveal universal A-site splitting in LiNbO3-type structures with mixed multivalent B/B', or anionic sites, and the splitting-atomic displacement can be strongly suppressed by magnetic interactions and/or hybridization of valence bands between d electrons of the A- and B-site cations.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 15
Times cited: 1
DOI: 10.1021/JACS.0C01814
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“B-site ordered perovskite LaSrMnNbO6 : synthesis, structure and antiferromagnetism”. Yang T, Perkisas T, Hadermann J, Croft M, Ignatov A, Greenblatt M, Journal of solid state chemistry 183, 2689 (2010). http://doi.org/10.1016/j.jssc.2010.08.041
Abstract: LaSrMnNbO6 has been synthesized by high temperature solid state reaction under 1% H2/Ar dynamic flow. The structure is determined by Rietveld refinement of the powder X-ray diffraction data. It crystallizes in the monoclinic space group P21/n with the unit cell parameters: a=5.69187(12), b=5.74732(10), c=8.07018(15) Å and β=90.0504(29)°, which were also confirmed by electron diffraction. The Mn2+ and Nb5+ ions, whose valence states are confirmed by X-ray absorption near-edge spectroscopy, are almost completely ordered over the B-site (<1% inversion) of the perovskite structure due to the large differences of both cationic size (0.19 Å) and charge. The octahedral framework displays significant tilting distortion according to Glazers tilt system a−b−c+. Upon heating, LaSrMnNbO6 decomposes at 690 °C under O2 flow or at 775 °C in air. The magnetic susceptibility data indicate the presence of long-range antiferromagnetic ordering at TN=8 K; the experimentally observed effective paramagnetic moment, μeff=5.76 μB for high spin Mn2+ (3d5, S=5/2) is in good agreement with the calculated value (μcalcd=5.92 μB).
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 2.299
Times cited: 13
DOI: 10.1016/j.jssc.2010.08.041
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“High magnetic ordering temperature in the perovskites Sr4-xLaxFe3ReO12 (x=0.0, 1.0, 2.0)”. Retuerto M, Li MR, Go YB, Ignatov A, Croft M, Ramanujachary KV, Herber RH, Nowik I, Hodges JP, Dachraoui W, Hadermann J, Greenblatt M;, Journal of solid state chemistry 194, 48 (2012). http://doi.org/10.1016/j.jssc.2012.06.031
Abstract: A series of perovskites Sr4−xLaxFe3ReO12 (x=0.0, 1.0, 2.0) has been prepared by wet chemistry methods. The structure analyses by powder X-ray and neutron diffraction and electron microscopy show that these compounds adopt simple perovskite structures without cation ordering over the B sites: tetragonal (I4/mcm) for x=0.0 and 1.0 and orthorhombic (Pbmn) for x=2.0. The oxidation states of the cations in the compound with x=0.0 appear to be Fe3+/4+ and Re7+ and decrease for both with La substitution as evidenced by X-ray absorption spectroscopy. All the compounds are antiferromagnetically ordered above room temperature, as demonstrated by Mössbauer spectroscopy and the magnetic structures, which were determined by powder neutron diffraction. The substitution of Sr by La strongly affects the magnetic properties with an increase of TN up to ∼750 K.
Keywords: A1 Journal article; Electron microscopy for materials research (EMAT)
Impact Factor: 2.299
Times cited: 9
DOI: 10.1016/j.jssc.2012.06.031
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