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Title: Three-layer Aurivillius phases containing magnetic transition metal cations: Bi{sub 2-} {sub x} Sr{sub 2+} {sub x} (Nb,Ta){sub 2+} {sub x}M {sub 1-} {sub x} O{sub 12}, M=Ru{sup 4+}, Ir{sup 4+}, Mn{sup 4+}, x{approx}0.5

Abstract

We report the synthesis of Aurivillius-type phases incorporating magnetic M {sup 4+} cations (M=Mn, Ru, Ir), based on the substitution of M {sup 4+} for Ti{sup 4+} in Bi{sub 2}Sr{sub 2}(Nb,Ta){sub 2}TiO{sub 12}. Key to incorporating these magnetic transition metal cations appears to be the partial substitution of Sr{sup 2+} for Bi{sup 3+} in the {alpha}-PbO-type layer of the Aurivillius phase, leading to a concomitant decrease in the M {sup 4+} content; i.e., the composition of the prepared compounds was Bi{sub 2-} {sub x} Sr{sub 2+} {sub x} (Nb,Ta){sub 2+} {sub x}M {sub 1-} {sub x} O{sub 12}, x{approx}0.5. These compounds only exist over a narrow range of x, between an apparent minimum (x{approx}0.4) Sr{sup 2+} content in the {alpha}-PbO-type [Bi{sub 2}O{sub 2}] layer required for Aurivillius phases to form with magnetic M {sup 4+} cations, and an apparent maximum (x{approx}0.6) Sr{sup 2+} substitution in this [Bi{sub 2}O{sub 2}] layer. Rietveld-refinement of synchrotron X-ray powder diffraction data making use of anomalous dispersion at the Nb and Ru K edges show that the overwhelming majority of the incorporated M cations occupy the central of the three MO{sub 6} octahedral layers in the perovskite-type block. Magnetic susceptibility measurements are presented and discussedmore » in the context of the potential for multiferroic (magnetoelectric) properties in these materials. - Graphical abstract: Structure of Bi{sub 1.5}Sr{sub 2.5}Nb{sub 2.5}Ru{sub 0.5}O{sub 12}.« less

Authors:
 [1];  [2];  [1];  [1];  [1];  [3]
  1. School of Chemistry, University of Sydney, Sydney, NSW 2006 (Australia)
  2. School of Chemistry, University of Sydney, Sydney, NSW 2006 (Australia) and Bragg Institute, ANSTO, PMB 1, Menai, NSW 2234 (Australia), E-mail: c.ling@chem.usyd.edu.au
  3. X-ray Operations and Research Division, Advanced Photon Source, Argonne National Laboratory, Argonne, IL 60439 (United States)
Publication Date:
OSTI Identifier:
21015659
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 180; Journal Issue: 1; Other Information: DOI: 10.1016/j.jssc.2006.10.031; PII: S0022-4596(06)00578-0; Copyright (c) 2006 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BISMUTH COMPOUNDS; BISMUTH IONS; CATIONS; IRIDIUM COMPOUNDS; IRIDIUM IONS; LAYERS; MAGNETIC SUSCEPTIBILITY; MANGANESE COMPOUNDS; MANGANESE IONS; NIOBIUM COMPOUNDS; OXIDES; PEROVSKITE; RUTHENIUM COMPOUNDS; RUTHENIUM IONS; STRONTIUM COMPOUNDS; STRONTIUM IONS; SYNCHROTRON RADIATION; SYNTHESIS; TANTALUM COMPOUNDS; TITANIUM IONS; X-RAY DIFFRACTION

Citation Formats

Sharma, Neeraj, Ling, Chris D., Wrighter, Grant E., Chen, Parry Y., Kennedy, Brendan J., and Lee, Peter L. Three-layer Aurivillius phases containing magnetic transition metal cations: Bi{sub 2-} {sub x} Sr{sub 2+} {sub x} (Nb,Ta){sub 2+} {sub x}M {sub 1-} {sub x} O{sub 12}, M=Ru{sup 4+}, Ir{sup 4+}, Mn{sup 4+}, x{approx}0.5. United States: N. p., 2007. Web. doi:10.1016/j.jssc.2006.10.031.
Sharma, Neeraj, Ling, Chris D., Wrighter, Grant E., Chen, Parry Y., Kennedy, Brendan J., & Lee, Peter L. Three-layer Aurivillius phases containing magnetic transition metal cations: Bi{sub 2-} {sub x} Sr{sub 2+} {sub x} (Nb,Ta){sub 2+} {sub x}M {sub 1-} {sub x} O{sub 12}, M=Ru{sup 4+}, Ir{sup 4+}, Mn{sup 4+}, x{approx}0.5. United States. doi:10.1016/j.jssc.2006.10.031.
Sharma, Neeraj, Ling, Chris D., Wrighter, Grant E., Chen, Parry Y., Kennedy, Brendan J., and Lee, Peter L. Mon . "Three-layer Aurivillius phases containing magnetic transition metal cations: Bi{sub 2-} {sub x} Sr{sub 2+} {sub x} (Nb,Ta){sub 2+} {sub x}M {sub 1-} {sub x} O{sub 12}, M=Ru{sup 4+}, Ir{sup 4+}, Mn{sup 4+}, x{approx}0.5". United States. doi:10.1016/j.jssc.2006.10.031.
@article{osti_21015659,
title = {Three-layer Aurivillius phases containing magnetic transition metal cations: Bi{sub 2-} {sub x} Sr{sub 2+} {sub x} (Nb,Ta){sub 2+} {sub x}M {sub 1-} {sub x} O{sub 12}, M=Ru{sup 4+}, Ir{sup 4+}, Mn{sup 4+}, x{approx}0.5},
author = {Sharma, Neeraj and Ling, Chris D. and Wrighter, Grant E. and Chen, Parry Y. and Kennedy, Brendan J. and Lee, Peter L.},
abstractNote = {We report the synthesis of Aurivillius-type phases incorporating magnetic M {sup 4+} cations (M=Mn, Ru, Ir), based on the substitution of M {sup 4+} for Ti{sup 4+} in Bi{sub 2}Sr{sub 2}(Nb,Ta){sub 2}TiO{sub 12}. Key to incorporating these magnetic transition metal cations appears to be the partial substitution of Sr{sup 2+} for Bi{sup 3+} in the {alpha}-PbO-type layer of the Aurivillius phase, leading to a concomitant decrease in the M {sup 4+} content; i.e., the composition of the prepared compounds was Bi{sub 2-} {sub x} Sr{sub 2+} {sub x} (Nb,Ta){sub 2+} {sub x}M {sub 1-} {sub x} O{sub 12}, x{approx}0.5. These compounds only exist over a narrow range of x, between an apparent minimum (x{approx}0.4) Sr{sup 2+} content in the {alpha}-PbO-type [Bi{sub 2}O{sub 2}] layer required for Aurivillius phases to form with magnetic M {sup 4+} cations, and an apparent maximum (x{approx}0.6) Sr{sup 2+} substitution in this [Bi{sub 2}O{sub 2}] layer. Rietveld-refinement of synchrotron X-ray powder diffraction data making use of anomalous dispersion at the Nb and Ru K edges show that the overwhelming majority of the incorporated M cations occupy the central of the three MO{sub 6} octahedral layers in the perovskite-type block. Magnetic susceptibility measurements are presented and discussed in the context of the potential for multiferroic (magnetoelectric) properties in these materials. - Graphical abstract: Structure of Bi{sub 1.5}Sr{sub 2.5}Nb{sub 2.5}Ru{sub 0.5}O{sub 12}.},
doi = {10.1016/j.jssc.2006.10.031},
journal = {Journal of Solid State Chemistry},
number = 1,
volume = 180,
place = {United States},
year = {Mon Jan 15 00:00:00 EST 2007},
month = {Mon Jan 15 00:00:00 EST 2007}
}
  • We report the synthesis of Aurivillius-type phases incorporating magnetic M{sup 4+} cations (M=Mn, Ru, Ir), based on the substitution of M{sup 4+} for Ti{sup 4+} in Bi{sub 2}Sr{sub 2}(Nb,Ta){sub 2}TiO{sub 12}. The key to incorporating these magnetic transition metal cations appears to be the partial substitution of Sr{sup 2+} for Bi{sup 3+} in the {alpha}-PbO-type layer of the Aurivillius phase, leading to a concomitant decrease in the M{sup 4+} content; i.e., the composition of the prepared compounds was Bi{sub 2-x}Sr{sub 2+x}(Nb,Ta){sub 2+x}M{sub 1-x}O{sub 12}, x {approx} 0.5. These compounds only exist over a narrow range of x, between an apparentmore » minimum (x {approx} 0.4) Sr{sup 2+} content in the {alpha}-PbO-type [Bi{sub 2}O{sub 2}] layer required for Aurivillius phases to form with magnetic M{sup 4+} cations, and an apparent maximum (x {approx} 0.6) Sr{sup 2+} substitution in this [Bi{sub 2}O{sub 2}] layer. Rietveld-refinement of synchrotron X-ray powder diffraction data making use of anomalous dispersion at the Nb and Ru K edges show that the overwhelming majority of the incorporated M cations occupy the central of the three MO{sub 6} octahedral layers in the perovskite-type block. Magnetic susceptibility measurements are presented and discussed in the context of the potential for multiferroic (magnetoelectric) properties in these materials.« less
  • This work is dedicated to investigation of new disordered bismuth-containing oxy-phosphates compounds with an original structure type. As previously observed in this series, they are formed of [M{sub 4}Bi{sub 2n-2}O{sub 2n}]{sup x+} polycationic ribbons of width n O(Bi,M){sub 4} tetrahedra, surrounded by PO{sub 4} groups. In the new crystal structure type, double (=D), triple (=T) and tunnels (=t) alternate along a common axis obeying the TtDtTtDt/TTtTTt sequence in respect to a nomenclature previously described and recalled in this work. The existence this new polymorph has first been detected by electron diffraction in a multi-phased sample. Then, the crystal structure type,more » i.e., the TtDtTtDt/TTtTTt sequence, has been deduced from HREM images help to a contrast-interpreting code available for these series of polycations-formed compounds. The subsequent compounds formulation leads to a number of new materials that verify the general formula: [Bi{sub 2}(Bi,M){sub 4}O{sub 4}]{sub 2} [Bi{sub 4}(Bi,M){sub 4}O{sub 6}]{sub 6} (PO{sub 4}){sub 28} M{sub x}, with x=<12 and M=Cu{sup 2+}, Cd{sup 2+} cations. Single crystals of the nominal [O6Bi{sub 4.57}Cd{sub 3.43}]{sub 4}{sup +8.57} [O{sub 6}Bi{sub 4}Cd{sub 4}]{sub 2}{sup +8} [O{sub 4}Bi{sub 2}Cd{sub 3.56}Cu{sub 0.44}]{sub 2}{sup +6} (PO{sub 4}){sub 28} Cu{sub 10.86} have been prepared in a further stage and confirms the predicted crystal structure, Bi{sub {approx}}{sub 3.785}Cd{sub {approx}}{sub 3.575}Cu{sub {approx}}{sub 1.5}(PO{sub 4}){sub 3.5}O{sub 5.5}= , a=11.506(8)A, b=5.416(4)A, c=53.94 (4)A, {beta}=90.10(1){sup o}, RF=0.0835, RwF=0.0993, SG=A2/m, Z=8. As already observed for other elements of this family such as Bi{sub {approx}}{sub 1.2}M{sub {approx}}{sub 1.2}O{sub 1.5}(PO{sub 4}), Bi{sub {approx}}{sub 6.2}Cu{sub {approx}}{sub 6.2}O{sub 8}(PO{sub 4}){sub 5} or Bi{sub {approx}}{sub 3}Cd{sub {approx}}{sub 3.72}M{sub {approx}}{sub 1.28}O{sub 5}(PO{sub 4}){sub 3} (M=Cu, Co, Zn), this compound shows an additional example of PO{sub 4} disorder due to the presence of mixed Bi{sup 3+}/M{sup 2+} sites at the edges of ribbons. The origin and consequence of this so-called disorder mostly occurring on PO{sub 4} configurations is intensively discussed and has been characterized by infrared spectroscopy and by neutron diffraction on similar compounds. It is noticeable that the great number of antagonist PO{sub 4} configurations may order along the b-axis within a large periodicity which involves incommensurate lattice.« less
  • Ferroelectric Sr{sub 1-x}Ba{sub x}Bi{sub 2}(Nb{sub 0.5}Ta{sub 0.5}){sub 2}O{sub 9} and Sr{sub 0.5}Ba{sub 0.5}Bi{sub 2}(Nb{sub 1-y}Ta{sub y}){sub 2}O{sub 9} were synthesized by solid state reaction route. X-ray diffraction studies confirm the formation of single phase layered perovskite solid solutions over a wide range of compositions (x=y=0.0, 0.25, 0.50, 0.75 and 1). The lattice parameters and the Curie temperature (T{sub c}) have been found to have linear dependence on x and y. Transmission electron microscopy (TEM) suggest the lowering of orthorhombic distortion with increasing Ba{sup 2+} substitution. Variations in microstructural features as a function of x and y were monitored by scanningmore » electron microscopy (SEM). The dielectric constant at room temperature increases with increase in both x and y. Interestingly Ba{sup 2+} substitution on Sr{sup 2+} site induces diffused phase transition and diffuseness increases with increasing Ba{sup 2+} concentration.« less
  • New pyrochlore phases can be obtained in the systems Bi/sub 2-x/M/sub x/Ru/sub 2-y/Ir/sub y/O/sub 7-z/ by partial substitution of M (M=Mg, Ca, Sr, Co, Cu) for Bi/sup 3+/. The high electric conductivity and the insolubility in mineral acids and bases are preserved for all pyrochlore phases.