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Use of Refractory-Volatile Element Deep Eutectic Regions to Grow Single Crystalline Intermetallic Compounds

Compounds containing both refractory and volatile elements present a unique challenge for crystal growth, given the conflicting realities of high melting temperatures and high vapor pressures. Nevertheless, the discovery of superconductivity in FeAs and FeSe based materials and a Weyl semimetal state in TaP are motivations to explore compounds containing such pairs. Here, we discuss use of the low-melting single phase liquid regions above deep M-X eutectics (M=transition metal, X=P, S) as the basis for high temperature solutions for growing intermetallic compounds containing volatile-refractory pairs. We show that Ni-P, Pd-P, Pt-P, and Pd-S compositions form single phase melts at moderate temperatures below 1000 °C and with minimal vapor pressure. We first present the simple case of growing Ni 2 P from Ni-P and next discuss the more complicated growth of RPd 3 S 4 (R=La, Ce, Nd, Eu) from a Pd-S melt. We show how frit-disc alumina crucible sets allow for contamination-free capture of decanted liquid and its reuse in subsequent experiments, demonstrating a fractionation of the CePd 3 S 4 growth to determine the optimal conditions for crystal growth. We conclude by using the single phase liquid regions above the Pt-P and Pd-P eutectics to grow single crystals of MPt 5 P (M=Mn, Fe) and MnPd 5 P. As these materials have primarily been studied in polycrystalline form, we give an overview of the magnetic and transport properties of our single crystals. The examples outlined here illustrate the utility of using the single phase liquid above deep metal-X eutectics for solution growth and materials discovery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗

Materials Data on PdS2 by Materials Project

PdS2 crystallizes in the orthorhombic Pbca space group. The structure is two-dimensional and consists of two PdS2 sheets oriented in the (0, 0, 1) direction. Pd4+ is bonded in a square co-planar geometry to four equivalent S2- atoms. There are two shorter (2.34 Å) and two longer (2.35 Å) Pd–S bond lengths. S2- is bonded in a distorted trigonal non-coplanar geometry to two equivalent Pd4+ and one S2- atom. The S–S bond length is 2.10 Å.

36 MATERIALS SCIENCE↗

Materials Data on PdS by Materials Project

PdS crystallizes in the tetragonal P4_2/m space group. The structure is three-dimensional. there are three inequivalent Pd2+ sites. In the first Pd2+ site, Pd2+ is bonded in a rectangular see-saw-like geometry to four equivalent S2- atoms. There are two shorter (2.37 Å) and two longer (2.38 Å) Pd–S bond lengths. In the second Pd2+ site, Pd2+ is bonded in a rectangular see-saw-like geometry to four equivalent S2- atoms. All Pd–S bond lengths are 2.37 Å. In the third Pd2+ site, Pd2+ is bonded in a distorted square co-planar geometry to four equivalent S2- atoms. All Pd–S bond lengths are 2.34 Å. S2- is bonded to four Pd2+ atoms to form a mixture of distorted corner and edge-sharing SPd4 trigonal pyramids.

36 MATERIALS SCIENCE↗

Materials Data on Pd16S7 by Materials Project

Pd16S7 crystallizes in the cubic I-43m space group. The structure is three-dimensional and consists of two Pd16S7 frameworks. there are two inequivalent Pd sites. In the first Pd site, Pd is bonded in a linear geometry to two S atoms. There are one shorter (2.29 Å) and one longer (2.34 Å) Pd–S bond lengths. In the second Pd site, Pd is bonded in a distorted trigonal non-coplanar geometry to three equivalent S atoms. All Pd–S bond lengths are 2.51 Å. There are two inequivalent S sites. In the first S site, S is bonded to four equivalent Pd atoms to form distorted corner-sharing SPd4 trigonal pyramids. In the second S site, S is bonded to six Pd atoms to form distorted SPd6 pentagonal pyramids that share corners with three equivalent SPd4 trigonal pyramids and edges with three equivalent SPd6 pentagonal pyramids.

36 MATERIALS SCIENCE↗

Materials Data on Pd3S by Materials Project

Pd3S crystallizes in the orthorhombic Cmcm space group. The structure is three-dimensional. there are two inequivalent Pd sites. In the first Pd site, Pd is bonded in a bent 150 degrees geometry to two equivalent S atoms. There are one shorter (2.36 Å) and one longer (2.43 Å) Pd–S bond lengths. In the second Pd site, Pd is bonded in a linear geometry to two equivalent S atoms. Both Pd–S bond lengths are 2.32 Å. S is bonded in a 6-coordinate geometry to six Pd atoms.

36 MATERIALS SCIENCE↗

Materials Data on Pd4S by Materials Project

Pd4S crystallizes in the tetragonal P-42_1c space group. The structure is three-dimensional. Pd is bonded in a distorted bent 150 degrees geometry to two equivalent S atoms. There are one shorter (2.37 Å) and one longer (2.51 Å) Pd–S bond lengths. S is bonded in a 8-coordinate geometry to eight equivalent Pd atoms.

36 MATERIALS SCIENCE↗