Crystal growth and characterization of the transition-metal phosphides copper diphosphide, nickel diphosphide, and rhodium triphosphide

Odile, J. P.; Soled, S.; Castro, Cristina; Wold, A.

doi:10.1021/ic50180a018

Cited by 66 publications

(54 citation statements)

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“…The electrical properties of CuP 2 have been previously measured and despite the high reported electrical resistivity (r = 126 mO cm at 300 K) due to a low carrier concentration, the experimental p-PF is in the range of a good TE material due to a large Seebeck coefficient. 91 The reported electrical properties even exceed the computed values (Table 1). In addition to the favourable predicted electrical properties, the thermal conductivity of CuP 2 is reduced by a factor of two compared to IrP 2 , enhancing the TE performance (Table S6, ESI †).…”

mentioning

confidence: 80%

“…While the electronic properties of single-crystalline m-NiP 2 were previously measured by Odile et al showing a high resistivity and Seebeck coefficient (Table 1), 91 the electronic properties of c-NiP 2 were unknown. In the present study, the transport properties of c-NiP 2 were determined from 2 K to 725 K (experimental data are listed in Tables S13-S15 in ESI †).…”

Section: à2mentioning

confidence: 91%

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Metal phosphides as potential thermoelectric materials

et al. 2017

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There still exists a crucial need for new thermoelectric materials to efficiently recover waste heat as electrical energy. Although metal phosphides are stable and can exhibit excellent electronic properties, they have traditionally been overlooked as thermoelectrics due to expectations of displaying high thermal conductivity. Based on high-throughput computational screening of the electronic properties of over 48 000 inorganic compounds, we find that several metal phosphides offer considerable promise as thermoelectric materials, with excellent potential electronic properties (e.g. due to multiple valley degeneracy). In addition to the electronic band structure, the phonon dispersion curves of various metal phosphides were computed indicating low-frequency acoustic modes that could lead to low thermal conductivity. Several metal phosphides exhibit promising thermoelectric properties. The computed electronic and thermal properties were compared to experiments to test the reliability of the calculations indicating that the predicted thermoelectric properties are semi-quantitative. As a complete experimental study of the thermoelectric properties in MPs, cubic-NiP 2 was synthesized and the low predicted lattice thermal conductivity (B1.2 W m À1 K À1 at 700 K) was confirmed. The computed Seebeck coefficient is in agreement with experiments over a range of temperatures and the phononic dispersion curve of c-NiP 2 is consistent with the experimental heat capacity. The predicted high thermoelectric performance in several metal phosphides and the low thermal conductivity measured in NiP 2 encourage further investigations of thermoelectric properties of metal phosphides.

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confidence: 80%

Section: à2mentioning

confidence: 91%

Metal phosphides as potential thermoelectric materials

et al. 2017

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“…[3][4][5][6][7][8][9][10][11][12][13] While some of them seem to have substantial optical band gaps ͑0.45 and 1.4 eV for CoP 3 and IrSb 3 , respectively͒, 3,7 no optical gap is found for CoAs 3 and CoSb 3 .…”

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confidence: 99%

Electronic structure and bonding in skutterudite-type phosphides

et al. 1996

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The electronic structures of the skutterudite-type phosphides CoP 3 and NiP 3 have been investigated by means of first-principles linear muffin-tin orbital-atomic sphere approximation band-structure calculations. The presence of P 4 rings in the skutterudite structure is of great importance in determining the nature of the electronic bands around the Fermi level, composed mainly of -type molecular orbitals of these units. The metallic character found for NiP 3 should be ascribed to the phosphorus framework rather than to the metal atoms.The skutterudite ͑i.e., CoAs 3 -type͒ structure is found for a number of binary transition-metal pnictides M X 3 ͑Ref. 1͒, with interesting electronic properties that suggest their use as advanced thermoelectric materials.2,3 Except for NiP 3 , all other known compounds in this family ͑M X 3 with M ϭCo, Rh, Ir and XϭP, As, Sb͒ are isoelectronic and have been found to behave as diamagnetic p-type semiconductors. [3][4][5][6][7][8][9][10][11][12][13] While some of them seem to have substantial optical band gaps ͑0.45 and 1.4 eV for CoP 3 and IrSb 3 , respectively͒, 3,7 no optical gap is found for CoAs 3 and CoSb 3 .7 NiP 3 , the only known skutterudite 14,15 of a group-10 metal, shows metallic behavior with Pauli-type paramagnetism. 13Closely related crystal structures are found for the ternary compounds RM 4 X 12 ͑Rϭrare-earth metal, M ϭFe, Ru, Os, and XϭP, As, Sb͒. In these, the M 4 X 12 subnet adopts the skutterudite structure, [16][17][18][19] while the rare-earth metal atoms occupy the cubic positions that are empty in the binary phases. The physical properties of the ternary phosphides LaM 4 P 12 are specially interesting, being superconductors with transition temperatures T c ϭ4.1, 7.2, and 1.8 K for M ϭFe, Ru, and Os, 20 respectively. Although these compounds show interesting physical properties, relatively little is known about their electronic structure, probably because of the complex crystal structure with a relatively open unit cell. So far, only two bandstructure calculations have been reported for the skutteruditetype compounds. In the first study, 21 the electronic structures of LaFe 4 P 12 and related compounds were analyzed by using the extended Hückel tight-binding ͑EHTB͒ method. Recently, self-consistent band-structure calculations, using the linear augmented plane-wave method for IrSb 3 , CoAs 3 , and CoSb 3 , have been published by Singh and Pickett. 22 In this contribution, we report first-principles bandstructure calculations using the linear muffin-tin orbital method in the atomic sphere approximation ͑LMTO-ASA͒ ͑Refs. 23-25͒ to explore the band structure of CoP 3 and NiP 3 . CRYSTAL STRUCTUREThe nature of the highest occupied bands, responsible for the electronic properties of a material, is strongly dependent on its crystal structure. A detailed knowledge of the crystal structure is, therefore, indispensable before analyzing the details of the electronic structure. In the case of the skutterudite structure ͑space-group Im3, n. 204͒, 26 the convention...

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“…These are classified into two groups according to their electronic properties; La 0.6 Rh 4 P 12 is a superconductor, while La 0.5 Rh 4 As 12 and La 0.5 Rh 4 Sb 12 are semiconductors with E g = 0.03 eV [12] and E g > 0.08 eV, respectively. The corresponding unfilled skutterudites are similarly classified; an unfilled skutterudite RhP 3 , which corresponds to La 0.6 Rh 4 P 12 , has been experimentally determined to be a metal [20,21]. RhAs 3 and RhSb 3 , which correspond to La 0.5 Rh 4 As 12 and La 0.5 Rh 4 Sb 12 , respectively, are semiconductors with E g > 0.85 eV [22] and E g = 0.8 eV [23,24], respectively.…”

Section: Discussionmentioning

confidence: 99%

Electrical and magnetic properties of La0.5Rh4Sb12 filled skutterudite synthesized at high pressure

Ibuka

Imai

Miyakawa

et al. 2015

Journal of Alloys and Compounds

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A filled skutterudite, La 0.5 Rh 4 Sb 12 , with a lattice constant of 9.284(2)Å was synthesized using a high-pressure technique. The electrical resistivity showed semiconducting behavior and the energy gap was estimated to be more than 0.08 eV. Magnetic susceptibility measurements indicated temperatureindependent diamagnetism, which originates from Larmor diamagnetism. The electrical properties of this compound are more similar to those of the La 0.5 Rh 4 As 12 semiconductor with an energy gap of 0.03 eV than to those of the La 0.6 Rh 4 P 12 superconductor.

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Crystal growth and characterization of the transition-metal phosphides copper diphosphide, nickel diphosphide, and rhodium triphosphide

Cited by 66 publications

References 10 publications

Metal phosphides as potential thermoelectric materials

Metal phosphides as potential thermoelectric materials

Electronic structure and bonding in skutterudite-type phosphides

Electrical and magnetic properties of La0.5Rh4Sb12 filled skutterudite synthesized at high pressure

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