Electrical conductivity and superconductivity of metal phosphides with skutterudite-type structure prepared at high pressure

Shirotani, Ichimin; Adachi, Takafumi; Tachi, Kenji; Todo, Synge; Nozawa, K.; Yagi, T.; Kinoshita, Minoru

doi:10.1016/0022-3697(95)00197-2

Cited by 98 publications

(35 citation statements)

References 13 publications

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“…An exception to this is the binary NiP 3 , which in the Dudkin model has an "excess" of one electron, thereby giving metallic conduction. This is confirmed by experimental 33 and theoretical 6 investigations.…”

Section: Discussionsupporting

confidence: 61%

Transition metald-band occupancy in skutterudites studied by electron energy-loss spectroscopy

et al. 2007

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The transition-metal 3d occupancy of a series of thermoelectric skutterudites is investigated using electron energy-loss spectroscopy. We find that bonding causes an emptying of the 3d states in the binary skutterudites CoP 3 , CoAs 3 , CoSb 3 , and NiP 3 , while compared to the pure Fe the 3d occupancy in LaFe 4 P 12 is significantly increased, consistent with the idea that each interstitial La atom ͑rattler͒ donates three electrons to compensate for missing valence electron of Fe as compared to Co. These experimental results are in agreement with previous models suggesting a predominantly covalent bonding between transition metal and pnictogen atoms in skutterudites, and provide evidence of charge transfer from La to the Fe-P complex in LaFe 4 P 12 .

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Section: Discussionsupporting

confidence: 61%

Transition metald-band occupancy in skutterudites studied by electron energy-loss spectroscopy

et al. 2007

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“…Because they make very good thermoelectrics 21,22,47 , host unusual metalinsulator transitions [23][24][25] , can be rare-earth magnets, heavyfermion compounds [26][27][28][29][30] , non-Fermi liquids [31][32][33][34][35] , itinerant ferromagnets [36][37][38] and superconductors 27,[39][40][41][42][43][44][45][46] , and have been proposed as topological insulators 48 , filled skutterudites are a very important class of non-molecular solids. Because the electronic and magnetic properties of solids depend critically on the actual atoms making up the compounds in addition to the compound's electron count, expanding the filled skutterudites from primarily group 8 to group 9 metal-based compounds, as we have done in this study, affords the opportunity to observe many new physical properties.…”

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confidence: 99%

A large family of filled skutterudites stabilized by electron count

et al. 2015

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The Zintl concept is important in solid-state chemistry to explain how some compounds that combine electropositive and main group elements can be stable at formulas that at their simplest level do not make any sense. The electronegative elements in such compounds form a polyatomic electron-accepting molecule inside the solid, a 'polyanion', that fills its available energy states with electrons from the electropositive elements to obey fundamental electroncounting rules. Here we use this concept to discover a large family of filled skutterudites based on the group 9 transition metals Co, Rh, and Ir, the alkali, alkaline-earth, and rare-earth elements, and Sb 4 polyanions. Forty-three new filled skutterudites are reported, with 63 compositional variations-results that can be extended to the synthesis of hundreds of additional new compounds. Many interesting electronic and magnetic properties can be expected in future studies of these new compounds.

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“…As Fe (Ru) is substituted for Ru (Fe), T SC is largely suppressed and exhibits a discontinuity or a minimum around x = 0.75. While both LaRu 4 P 12 and LaFe 4 P 12 are believed to be s-wave superconductors [8][9][10][11], two types of superconductivity seem to compete with one another. The superconductivity of Os-doped system La(Ru 1−x Os x ) 4 P 12 has been studied previously [8].…”

Section: Methodsmentioning

confidence: 99%

“…While both LaRu 4 P 12 and LaFe 4 P 12 are believed to be s-wave superconductors [8][9][10][11], two types of superconductivity seem to compete with one another. The superconductivity of Os-doped system La(Ru 1−x Os x ) 4 P 12 has been studied previously [8]. LaOs 4 P 12 has a low T SC of 1.8 K. However, the T SC of LaRu 2 Os 2 P 12 coincides with the T SC (7.2K) of LaRu 4 P 12 even though 50% of Ru atoms are substituted with Os atoms.…”

Section: Methodsmentioning

confidence: 99%

Fe Substitution Effect on Filled Skutterudite Superconductor LaRu₄P₁₂

Kawaai¹,

Kawamura²,

Hayashi³

et al. 2014

Proceedings of the International Conference on Strongly Correlated Electron Systems (SCES2013)

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Filled skutterudite compounds include nineteen superconductors. While most of filled skutterudite superconductors including LaRu 4 P 12 (a superconductivity transition temperature T SC = 7.2 K) show negative pressure dependences of T SC , LaFe 4 P 12 with T SC = 4.1 K has a positive pressure dependence of T SC . In order to elucidate the reason for the deference of pressure dependence of T SC between LaFe 4 P 12 and LaRu 4 P 12 , we have synthesized La(Ru 1−x Fe x ) 4 P 12 (x = 0.25, 0.5, 0.75 and 0.9) under high pressure and studied Fe-substitution effect on superconductivity of LaRu 4 P 12 by means of DC magnetization measurements. T SC decreases with increasing Fe substitution x. La(Ru 0.25 Fe 0.75 ) 4 P 12 shows no superconductivity down to 2 K. The suppression ratio of T SC is much larger than expected chemical pressure effect. The change of electrical density of state at Fermi level could be dominant for the suppression of T SC .

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Electrical conductivity and superconductivity of metal phosphides with skutterudite-type structure prepared at high pressure

Cited by 98 publications

References 13 publications

Transition metald-band occupancy in skutterudites studied by electron energy-loss spectroscopy

Transition metald-band occupancy in skutterudites studied by electron energy-loss spectroscopy

A large family of filled skutterudites stabilized by electron count

Fe Substitution Effect on Filled Skutterudite Superconductor LaRu₄P₁₂

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Electrical conductivity and superconductivity of metal phosphides with skutterudite-type structure prepared at high pressure

Cited by 98 publications

References 13 publications

Transition metald-band occupancy in skutterudites studied by electron energy-loss spectroscopy

Transition metald-band occupancy in skutterudites studied by electron energy-loss spectroscopy

A large family of filled skutterudites stabilized by electron count

Fe Substitution Effect on Filled Skutterudite Superconductor LaRu4P12

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Fe Substitution Effect on Filled Skutterudite Superconductor LaRu₄P₁₂