Synthesis and structural analysis of nonstoichiometric ternary fulleride K 1.5 Ba 0.25 CsC 60.

The existence of cation-vacancy sites in fullerides might lead to long-range ordering and generate a new vacancy-ordered superstructure. The purpose of this work is to search whether or not long-range ordering of vacant tetrahedral sites, namely superstructure emerges in nonstoichiometric K 1.5 Ba 0.25 CsC 60 fulleride. Therefore, K 1.5 Ba 0.25 CsC 60 with cation-vacancy sites is synthesized using a precursor method to avoid inadequate stoichiometry control and formation of impurity phases within the target composition. For this purpose, first, phase-pure K 6 C 60 , Ba 6 C 60 and Cs 6 C 60 precursors are synthesized. Stoichiometric quantities of these precursors are used for further reaction with C 60 to afford K 1.5 Ba 0.25 CsC 60 . Rietveld analysis of the high-resolution synchrotron X-ray powder diffraction data of the precursors and K 1.5 Ba 0.25 CsC 60 confirms that K 6 C 60 , Ba 6 C 60 and Cs 6 C 60 are single-phase and they crystallize in a body-centered-cubic structure ( Im 3) as reported in the literature. The analysis also shows that K 1.5 Ba 0.25 CsC 60 phase can be perfectly modeled using a face-centered cubic structure. No new peaks appear which could have implied the appearance of a superstructure. This suggests that there is no long-range ordered arrangement of vacant tetrahedral sites in K 1.5 Ba 0.25 CsC 60 .