Three ternary thiophosphates α-Ba2P2S6, β-Ba2P2S6, and Pb2P2S6, were synthesized via a high temperature salt flux method or an I2 transport reaction. β-Ba2P2S6 and Pb2P2S6 were previously structurally characterized without investigating...

Two acentric thiophosphate compounds, HfP2S6 and α-Ag4P2S6, are revisited and studied as infrared nonlinear optical materials. HfP2S6 and α-Ag4P2S6 were structurally characterized without any property measurements. In this work, HfP2S6...

Two type-I clathrates were synthesized by introducing Ga into the framework of the Ba8Cu16P30 type-I clathrate. The introduction of minute amounts of Ga, 1.9% Ga/ Mtotal (where Mtotal = Cu + Ga), resulted in the disturbance of the completely ordered Pbcn superstructure of Ba8Cu16P30. Ba8Cu15.43(2)Ga0.3P30.26(3) crystallizes in a partially ordered orthorhombic Pmna clathrate-I superstructure with five out of 15 framework sites being jointly occupied by metal+phosphorus. Increasing the Ga content resulted in all framework sites being occupied by metal + phosphorus in the archetype cubic Pm[Formula: see text] n clathrate-I crystal structure of Ba8Cu14.5(3)Ga1.3P30.2(4) with 8.2% Ga/ Mtotal. A combination of energy dispersive x-ray spectroscopy, inductively coupled plasma mass spectroscopy, and single crystal x-ray diffraction was used to determine the structures alongside the compositions. The positional disorder was verified by 31P solid state NMR spectroscopy. Characterization of the transport properties indicated that the Ga-substituted samples exhibit higher Seebeck coefficients and electrical resistivities compared to its pristine counterpart, in line with the expected reduction of the hole concentration due to Ga/Cu substitution. Moderate improvements in the thermoelectric power factor and overall figure-of-merit were observed for samples with 6.9% and 3.8% Ga/ Mtotal as compared to those for the pristine Ba8Cu16P30 clathrate. Band structure calculations shed light on how Ga substitution affects the electronic structure and thermoelectric properties of studied clathrates.

The zinc−antimony phase space has been heavily investigated due to the structural complexity and abundance of highperforming thermoelectric materials. Consequentially, the desire to use zinc and antimony as framework elements to encage rattling cations and achieve phonon-glass-electron-crystal-type properties has remained an enticing goal with only two alkali metal clathrates to date, Cs 8 Zn 18 Sb 28 and K 58 Zn 122 Sb 207 . Guided by Zintl electroncounting predictions, we explored the Ba−Zn−Pn (Pn = As, Sb) phase space proximal to the expected composition of the type-I clathrate. In situ powder X-ray diffraction studies revealed two "hidden" compounds which can only be synthesized in a narrow temperature range. The ex situ synthesis and crystal growth unveiled that instead of type-I clathrates, compositionally close but structurally different new clathrate-like compounds formed, Ba 2 Zn 5 As 6 and Ba 2 Zn 5 Sb 6 . These materials crystallize in a unique structure, in the orthorhombic space group Pmna with the Wyckoff sequence i 2 h 6 gfe. Single-phase synthesis enabled the exploration of their transport properties. Rattling of the Ba cations in oversized cages manifested low thermal conductivity, which, coupled with the high Seebeck coefficients observed, are prerequisites for a promising thermoelectric material. Potential for further optimization of the thermoelectric performance by aliovalent doping was computationally analyzed.