Eu<sub>4</sub>Bi<sub>3</sub>: Crystal Structure, Magnetic and Electronic Properties

Wang, Mary E.; Chang, Jimmy T.; Kauzlarich, Susan M.

doi:10.1002/zaac.19966220309

Cited by 12 publications

(4 citation statements)

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“…On the other hand, the electrodeless “Q” method gave ρ 298 = 38.1 μΩ·cm and a mean temperature dependence of 0.30(1)% K -1 for Eu 4 Bi 3 . This is much more in line with the behavior of Ba 4 Bi 3 than the evidently erroneous result reported earlier for Eu 4 Bi 3 , ρ 298 = 1.29(1) Ω·cm . Resistivity measurements on Ba 4 As 2.60 by the “Q” method were also attempted, but the resistivity was too large to give an answer by this method.…”

Section: Resultssupporting

confidence: 81%

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Valence Compounds versus Metals. Synthesis, Characterization, and Electronic Structures of Cubic Ae₄Pn₃ Phases in the Systems Ae = Ca, Sr, Ba, Eu; Pn = As, Sb, Bi

Mudring

Corbett

2003

Inorg. Chem.

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The isostructural compounds Sr 4 Bi 3 , Ba 4 Bi 3 , and Ba 4 As ∼2.60 were prepared by direct reactions of the corresponding elements and their structures determined from single-crystal X-ray diffraction data as antiTh 3 P 4 type in the cubic space group I43d, Z = 4 (a = 10.101(1) Å, 10.550(1) Å, 9.973 (1) Å, respectively). The two bismuth compounds are stoichiometric, and the arsenide refines as Ba 4 As 2.60(2) . Only unrelated phases are obtained for all binary combinations among the title components for either Ca or Sb. The magnetic susceptibility and resistivities of Ba 4 Bi 3 and Eu 4 Bi 3 show that they are good metallic conductors (∼40 μΩ·cm at 298 K), whereas Ba 4 As 2.60 exhibits ρ 150 > 1000 μΩ·cm. The electronic structures of Sr 4 Bi 3 , Ba 4 Bi 3 , and Ba 4 As 3 were calculated by TB-LMTO-ASA methods. Mixing of cation d states into somewhat disperse valence p bands on Bi results in empty bands at E F and metallic behavior, whereas the narrower valence band in the electron-deficient Ba 4 As 3 leads to vacancies in about 11% of the anion sites and a valence compound. Keywords Department of Chemistry Disciplines Metallurgy | Other Materials Science and Engineering | Process Control and Systems CommentsReprinted with permission from Inorg. Chem., 2003, 42 (21) The isostructural compounds Sr 4 Bi 3 , Ba 4 Bi 3 , and Ba 4 As ∼2.60 were prepared by direct reactions of the corresponding elements and their structures determined from single-crystal X-ray diffraction data as anti-Th 3 P 4 type in the cubic space group I4 h3d, Z ) 4 (a ) 10.101(1) Å, 10.550(1) Å, 9.973 (1) Å, respectively). The two bismuth compounds are stoichiometric, and the arsenide refines as Ba 4 As 2.60(2) . Only unrelated phases are obtained for all binary combinations among the title components for either Ca or Sb. The magnetic susceptibility and resistivities of Ba 4 Bi 3 and Eu 4 Bi 3 show that they are good metallic conductors (∼40 µΩ‚cm at 298 K), whereas Ba 4 As 2.60 exhibits F 150 > 1000 µΩ‚cm. The electronic structures of Sr 4 Bi 3 , Ba 4 Bi 3 , and Ba 4 As 3 were calculated by TB-LMTO-ASA methods. Mixing of cation d states into somewhat disperse valence p bands on Bi results in empty bands at E F and metallic behavior, whereas the narrower valence band in the electron-deficient Ba 4 As 3 leads to vacancies in about 11% of the anion sites and a valence compound.

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Section: Resultssupporting

confidence: 81%

“…Up to now, only a few pnictides with anti-Th 3 P 4 type structures have been reported with nominally divalent cations: Eu 4 Bi 3 , Ba 3 P 2 (≙Ba 4 P 2.67 ), and Ba 8 As 5 Au . In Ba 8 As 5 Au, five As -3 and one Au - are disordered over the single anion site.…”

Section: Introductionmentioning

confidence: 99%

Valence Compounds versus Metals. Synthesis, Characterization, and Electronic Structures of Cubic Ae₄Pn₃ Phases in the Systems Ae = Ca, Sr, Ba, Eu; Pn = As, Sb, Bi

Mudring

Corbett

2003

Inorg. Chem.

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“…Consistent with this interpretation, magnetic susceptibility measurements on Eu 14 InSb 11 show only one magnetic transition at about 15 K. 22 The magnitude of the transition temperature is consistent with that observed in other Eu 2+ -containing com-pounds. 40,41 The 15 K transition is reminescent of an antiferromagnetic ordering (zero field-cooled (ZFC)) which is suppressed upon application of field ((fieldcooled (FC) data). The hysteresis loop on powder samples shows a saturation moment of 102(1) µ B , in agreement with the assigned valencies.…”

Section: Resultsmentioning

confidence: 99%

Colossal Magnetoresistance in the Transition-Metal Zintl Compound Eu₁₄MnSb₁₁

Chan¹,

Kauzlarich²,

Klavins³

et al. 1997

Chem. Mater.

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106

108

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Magnetoresistance measurements have been carried out on single-crystal sample of the transition-metal Zintl compound Eu 14 MnSb 11 . Eu 14 MnSb 11 is the first compound of the Ca 14 -AlSb 11 structure type in which magnetoresistive effects have been measured. Colossal magnetoresistance (CMR) at 92 K and 5 T with ∆F/F(0) ) -36% and at 5 K and 5 T with ∆F/F(0) ) -42% were observed. CMR is observed at the ferromagnetic-paramagnetic phase transition (92 K). A large negative magnetoresistance is observed below the second magnetic transition (15 K) and is attributed to a field-induced antiferromagnetic-ferromagnetic ordering of the Eu 2+ lattice. The MR is highly anisotropic with respect to the crystallographic axes. A sign change in the curvatures of F(H) curves below and above 92 K has been observed, indicating that two different mechanisms are responsible for the magnetic scattering of the carriers in two separate temperature regions.

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“…In more general cases, the composition of ternary AB 2 C 2 can be extended to a broader range of variations, yet the materials maintain a crystal structure as shown in Figure . These crystallographic features lead to the interesting ductility, electrical properties, and thermal properties in Mg 3 Sb 2 and its derivative AB 2 C 2 compounds. Moreover, the allowance of formation of solid solutions in a large compositional range enables another degree of freedom for tuning the orbital, chemical bonds, defects, and occupation disordering to manipulate their transport properties.…”

Section: Crystallography Propertiesmentioning

confidence: 99%

Advances in Thermoelectric Mg₃Sb₂ and Its Derivatives

Shi

Wang

et al. 2018

Small Methods

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approaching their minimum, therefore fundamentally limits the availability for further improvements in these materials by this thermal strategy.This inspires the development of electronic strategies for zT enhancements in recent years. The strong coupling effect among S, σ, and κ e has led early strategies for electronic performance enhancement to mainly rely on the carrier concentration (n H ) optimization through chemical doping for nearly the past half of a century. [7] Till very recently, proven electronic strategies have been typified by engineering the band structure to increase the band degeneracy through band convergence [8] or nestification, [9] to decrease the band effective mass [10] and to introduce resonant states. [11] These approaches successfully decouple the strong correlation among electronic transport properties to some extent, enabling effective improvements in electronic performance for enhancing zT.The utilization of the above thermal and electronic strategies has led to a significant advancement mostly in conventional thermoelectrics such as PbTe [7,[12][13][14][15][16] and Bi 2 Te 3 , [17][18][19][20] while the toxicity and the scarcity of the constituent element are important issues limiting their large-scale application. Zintl compounds, which by strict definition requires to be valence balanced and semiconducting, [21] have shown excellent zT at high temperatures. [21][22][23][24] A recently developed class of Zintl compounds [25] having CaAl 2 Si 2 -type structure, Mg 3 Sb 2 , and its derivatives, demonstrates a great potential to address the toxicity and the scarcity issues and therefore attracts increasing number of researchers to focus on these materials. [26] The promising thermoelectric performance realized in these compounds is enabled by the richness in composition for further manipulation of both electronic and thermal properties as well as by the intrinsic low lattice thermal conductivity. The general formula for this class of Zintl compounds can be written as AB 2 C 2 , where A can be alkaline earth or rare-earth elements (e.g., Mg, [27][28][29] Ca, [30] Sr, [31,32] Ba, [33] Eu, [34] Yb [30] ), B can be transition metals or main-group elements (e.g., Cd, [35,36] Zn, [37] Mg, [38,39] Mn, [40] Al [41] ), and C can be Group IV/V elements (e.g., Sb, [29] Bi [42] ). Such a broad variety in composition enables either a very low lattice thermal conductivity [43][44][45][46] or a very high band degeneracy, [22,44,45] as well as great availabilities for further manipulating the phonon and charge transport properties through the formation of solid solution. [27,47] In this review, Mg 3 Sb 2 and its derivative (AB 2 C 2 ) compounds with demonstrated high thermoelectric performances are focused on. The origins leading to such a high performance are summarized Over the past couple of decades, thermoelectric Mg 3 Sb 2 and its derivatives have attracted increasing attention for thermoelectric applications. This is enabled by the richness in composition for manipulating both electronic and t...

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Eu₄Bi₃: Crystal Structure, Magnetic and Electronic Properties

Cited by 12 publications

References 20 publications

Valence Compounds versus Metals. Synthesis, Characterization, and Electronic Structures of Cubic Ae₄Pn₃ Phases in the Systems Ae = Ca, Sr, Ba, Eu; Pn = As, Sb, Bi

Valence Compounds versus Metals. Synthesis, Characterization, and Electronic Structures of Cubic Ae₄Pn₃ Phases in the Systems Ae = Ca, Sr, Ba, Eu; Pn = As, Sb, Bi

Colossal Magnetoresistance in the Transition-Metal Zintl Compound Eu₁₄MnSb₁₁

Advances in Thermoelectric Mg₃Sb₂ and Its Derivatives

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Eu4Bi3: Crystal Structure, Magnetic and Electronic Properties

Cited by 12 publications

References 20 publications

Valence Compounds versus Metals. Synthesis, Characterization, and Electronic Structures of Cubic Ae4Pn3 Phases in the Systems Ae = Ca, Sr, Ba, Eu; Pn = As, Sb, Bi

Valence Compounds versus Metals. Synthesis, Characterization, and Electronic Structures of Cubic Ae4Pn3 Phases in the Systems Ae = Ca, Sr, Ba, Eu; Pn = As, Sb, Bi

Colossal Magnetoresistance in the Transition-Metal Zintl Compound Eu14MnSb11

Advances in Thermoelectric Mg3Sb2 and Its Derivatives

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Eu₄Bi₃: Crystal Structure, Magnetic and Electronic Properties

Valence Compounds versus Metals. Synthesis, Characterization, and Electronic Structures of Cubic Ae₄Pn₃ Phases in the Systems Ae = Ca, Sr, Ba, Eu; Pn = As, Sb, Bi

Valence Compounds versus Metals. Synthesis, Characterization, and Electronic Structures of Cubic Ae₄Pn₃ Phases in the Systems Ae = Ca, Sr, Ba, Eu; Pn = As, Sb, Bi

Colossal Magnetoresistance in the Transition-Metal Zintl Compound Eu₁₄MnSb₁₁

Advances in Thermoelectric Mg₃Sb₂ and Its Derivatives