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5 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Single Crystal Growth of Synthetic Sulfide- and Phosphide-Based Minerals for Physical Measurements

In this work, we review recent advances in the use of high-temperature solution growth that allow for the growth of single crystalline samples of synthetic minerals. We outline how low-melting binary or ternary solutions are attractive solvents for solution growth and provide examples of the growth of bismuthinite (Bi 2 S 3 ), galena (PbS) and parkerite (Ni 3 Bi 2 S 2 ). We then focus on the Rh-S, Pd-S and Ni-P phase spaces to discuss how the low-melting regions near transition metal-main group eutectic compositions make excellent solvents for crystal growth of several binary and ternary minerals containing both high melting and volatile elements as well as for the discovery of new materials. We end by discussing the growth of synthetic canfieldite (Ag 8 SnS 6 ) and argyrodite (Ag 8 GeS 6 ) from Ag 2 S–Sn-S-based solutions.

58 GEOSCIENCES↗
DOE OSTI2020

Materials Data on Rh2S3 by Materials Project

Rh2S3 is Corundum-like structured and crystallizes in the orthorhombic Pbcn space group. The structure is three-dimensional. Rh3+ is bonded to six S2- atoms to form a mixture of face, edge, and corner-sharing RhS6 octahedra. The corner-sharing octahedra tilt angles range from 49–70°. There are a spread of Rh–S bond distances ranging from 2.33–2.43 Å. There are two inequivalent S2- sites. In the first S2- site, S2- is bonded to four equivalent Rh3+ atoms to form a mixture of distorted edge and corner-sharing SRh4 trigonal pyramids. In the second S2- site, S2- is bonded to four equivalent Rh3+ atoms to form a mixture of distorted edge and corner-sharing SRh4 tetrahedra.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on RhS2 by Materials Project

RhS2 is Pyrite structured and crystallizes in the cubic Pa-3 space group. The structure is three-dimensional. Rh4+ is bonded to six equivalent S2- atoms to form RhS6 octahedra that share corners with twelve equivalent RhS6 octahedra and corners with six equivalent SRh3S tetrahedra. The corner-sharing octahedral tilt angles are 65°. All Rh–S bond lengths are 2.43 Å. S2- is bonded to three equivalent Rh4+ and one S2- atom to form distorted SRh3S tetrahedra that share corners with three equivalent RhS6 octahedra and corners with fifteen equivalent SRh3S tetrahedra. The corner-sharing octahedral tilt angles are 76°. The S–S bond length is 2.18 Å.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Rh3S4 by Materials Project

Rh3S4 is Aluminum carbonitride-derived structured and crystallizes in the monoclinic C2/m space group. The structure is three-dimensional. there are four inequivalent Rh sites. In the first Rh site, Rh is bonded to six S atoms to form RhS6 octahedra that share corners with four equivalent RhS5 square pyramids, corners with two equivalent SRh3S tetrahedra, and edges with three RhS6 octahedra. There are a spread of Rh–S bond distances ranging from 2.34–2.39 Å. In the second Rh site, Rh is bonded to six S atoms to form RhS6 octahedra that share corners with two equivalent RhS5 square pyramids and edges with four equivalent RhS6 octahedra. There are two shorter (2.38 Å) and four longer (2.41 Å) Rh–S bond lengths. In the third Rh site, Rh is bonded to five S atoms to form RhS5 square pyramids that share corners with five RhS6 octahedra, corners with two equivalent SRh3S tetrahedra, and an edgeedge with one RhS5 square pyramid. The corner-sharing octahedra tilt angles range from 54–64°. There are a spread of Rh–S bond distances ranging from 2.30–2.42 Å. In the fourth Rh site, Rh is bonded in a distorted rectangular see-saw-like geometry to four S atoms. There are a spread of Rh–S bond distances ranging from 2.28–2.39 Å. There are four inequivalent S sites. In the first S site, S is bonded to three Rh and one S atom to form distorted SRh3S tetrahedra that share a cornercorner with one RhS6 octahedra, a cornercorner with one RhS5 square pyramid, and corners with twelve SRh3S tetrahedra. The corner-sharing octahedral tilt angles are 79°. The S–S bond length is 2.28 Å. In the second S site, S is bonded to four Rh atoms to form a mixture of distorted edge and corner-sharing SRh4 tetrahedra. In the third S site, S is bonded to four Rh atoms to form a mixture of edge and corner-sharing SRh4 tetrahedra. In the fourth S site, S is bonded to four Rh atoms to form a mixture of distorted edge and corner-sharing SRh4 tetrahedra.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Rh2S3 by Materials Project

Rh2S3 is Corundum structured and crystallizes in the trigonal R-3c space group. The structure is three-dimensional. Rh3+ is bonded to six equivalent S2- atoms to form a mixture of corner, edge, and face-sharing RhS6 octahedra. The corner-sharing octahedra tilt angles range from 47–61°. There are three shorter (2.37 Å) and three longer (2.41 Å) Rh–S bond lengths. S2- is bonded to four equivalent Rh3+ atoms to form a mixture of distorted corner and edge-sharing SRh4 trigonal pyramids.

36 MATERIALS SCIENCE↗