Single crystal studies of binary compounds Ta/Ga – A system with experimental and crystallographic peculiarities

We report on single crystal growth and characterisation of binary intermetallics TaxGay. Single crystals were obtained from mixtures of the elements which were handled under various conditions. Several new compounds were identified. The highest Ga-content is found for the new binary phases Ta6Ga31 and Ta8Ga41. Both compounds evolve as intergrown crystals. Ta8Ga41 belongs to the V8Ga41 type (R  3¯, Z=3, a=14.311 Å, c=15.344 Å), Ta6Ga31 to the triclinic Mo6Ga31-type (P  1¯, Z=2, a=9.697 Å, b=9.698 Å, c=14.879 Å, α=87.18°, β=80.83°, γ=85.18°). TaGa3 bases on the tetragonal TiAl3-type (I4/mmm, Z=2, a=3.769 Å, c=8.718 Å) but shows stacking faults leading to an increased Ta content Ta1+xGa3–x. This interpretation is supported by the structure model of an orthorhombic superstructure with an idealized composition Ta2Ga5 (Cmcm, Z=4, a=3.769, b=31.37, c=3.770 Å). Ta2–xGa5+x (x≈0.38) is a representative of the Mn2Hg5-type (P4/mbm, Z=2, a=9.3213(13), c=2.7572(6) Å). Ta4Ga5 represents a new compound with a novel crystal structure (P4/mbm, Z=16, a=11.793(2), c=16.967(3) Å). The complex structure contains polyhedra with coordination numbers between 11 and 14. Ta3Ga2 (P42/mnm, Z=2, a=6.8382(4), c=3.4963(2) Å) belongs to the U3Si2 type. For the composition Ta5Ga3 three different structure types were confirmed but with some differences. The tetragonal W5Si3 type (I4/mcm, Z=4, a=10.2199(7), c=5.1121(4) Å) is a stoichiometric binary compound, the hexagonal Mn5Si3-type (P63/mcm, Z=2, a=7.7023(4), c=5.3062(3) Å) contains a small amount of oxygen (Ta5Ga3O0.4) and in the tetragonal Cr5B3-type (I4/mcm, Z=4, a=6.5986(9), c=11.931(2)Å) one of the Ga-sites shows a significant underoccupation of 40% (“Ta2.2Ga”). Compositions were confirmed by EDX measurements.

Graphical abstractOctametic units of TaGa10 polyhedra form „supercubes“ in the Ga-rich alloys Ta6Ga31/Ta8Ga41. They are formed as single crystals from cooling Ga/Ta melts together with other Ta-Ga alloys like TaGa3/Ta1+xGa3–x, Ta2–xGa5+x, Ta4Ga5, Ta3Ga2, and Ta5Ga3.Figure optionsDownload full-size imageDownload as PowerPoint slide