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The phase stability of the (Bi2)m(Bi2Te3)n natural superlattices has beeninvestigated through the low temperature solid state synthesis of a number ofnew binary BixTe1-x compositions. Powder X-ray diffraction revealed that aninfinitely adaptive series forms for 0.44 < x < 0.70, while an unusual 2-phaseregion with continuously changing compositions is observed for 0.41 < x < 0.43.For x > 0.70, mixtures of elemental Bi and an almost constant composition(Bi2)m(Bi2Te3)n phase are observed. Rietveld analysis of synchrotron X-raypowder diffraction data collected on Bi2Te (m = 2, n = 1) revealed substantialinterchange of Bi and Te between the Bi2 and Bi2Te3 blocks, demonstrating thatthe block compositions are variable. All investigated phase pure compositionsare degenerate semiconductors with low residual resistivity ratios and moderatepositive magnetoresistances (R/R0 = 1.05 in 9 T). The maximum Seebeckcoefficient is +80 muV K-1 for x = 0.63, leading to an estimated thermoelectricfigure of merit, zT = 0.2 at 250 K.

Phase Stability, Structures and Properties of the (Bi2)m(Bi2Te3)n Natural Superlattices