Thermoelectric materials are special types of semiconductors that function as “heat pumps” and as heat-to-electricity converters. Thermoelectric power generation allows for small size, high reliability, and quiet operation. Efficient thermoelectric-based heat-to-electricity converters require higher performance materials than are currently available. Direct conversion of heat to electricity could be achieved with solidstate devices based on thermoelectric materials. These devices could play an important role in future energy production, conversion, management, and utilization. When a temperature gradient is created across a thermoelectric module, a voltage is generated, owing to the Seebeck effect. This voltage can be used to drive an external load. Currently, there is a strong scientific and technological drive to identify new materials with enhanced thermoelectric figures of merit ZT= (sS/k)T (where s is the electrical conductivity, S the thermopower or Seebeck coefficient, k the thermal conductivity, and T the temperature). The numerator sS is called the power factor PF. Several classes of materials are currently under investigation, including complex chalcogenides, doped PbTe and its solid solutions, such as Pb1 xSnxTe, [5,6] superlattice thin films, and quantum-dot superlattices. Also of interest are skutterudites, metal oxides, and intermetallic clathrates. The superlattice thin-film structures of Bi2Te3/Sb2Te3 grown from chemical vapor deposition, and of PbSe0.98Te0.02/PbTe formed by molecular beam epitaxy (MBE) have figures of merit greater than ZT= 2 (at approximately 300 and 550 K, respectively). The MBE-grown thin films PbSe0.98Te0.02/PbTe are n-type materials and contain pyramid-shaped “nanodots” of PbSe of uniform size (approximately 20 nm), which form spontaneously inside a matrix of PbTe. Because energyconversion applications require materials in large quantities, we seek bulk analogues of these systems with similar figures of merit. A recent contribution to these efforts was the discovery of the n-type Ag-based tellurides AgSbTe2/PbTe, which can exhibit high figures of merit (ZT 1.7 at 700 K) when properly doped. To construct a fully functioning optimal thermoelectric device, both nand p-type materials are needed. To date, there is no p-type counterpart to AgSbTe2/ PbTe with similar performance. The highest figure of merit reported for p-type bulk materials (ZT 1.2 at 700 K) is exhibited by the so-called TAGS system (based on Te, Ag, Ge, and Sb: (GeTe)1 x((Ag2Te)1 y(Sb2Te3)y)x). [23] These Ge-containing materials, though more efficient than PbTe, have found limited use, owing to their high cost and to a lowtemperature phase transition. Recently, we described the ptype materials Ag(Pb1 ySny)mSbTe2+m, which show outstanding thermoelectric properties, reaching a maximum figure of merit of ZT 1.45 at 630 K. Herein, we report that the Ag-free system Na1 xPbmSbyTem+2, with appropriate combinations of m, y, and x, achieves record-high ZT values for a p-type bulk thermoelectric material. The effect of the composition on the thermoelectric properties is profound. We show that the high performance of these materials derives mainly from a low thermal conductivity. High-resolution transmission electron microscopy (HRTEM) demonstrates pervasive nanostructuring in Na1 xPbmSbyTem+2, which may be the root cause for the remarkably low thermal conductivity. The Na1 xPbmSbyTem+2 system was selected for study because it should be naturally prone to create Na,Sb-rich clusters in the lattice. The distribution of Na and Sb ions in the Pb sublattice cannot be random, as would be demanded by a solid solution, because Coulombic forces alone tend to drive the system to clustering at the nanoscale, thereby lowering the overall energy. The results described herein are in agreement with long-standing theoretical predictions that nanostructuring in semiconductors would lead to enhanced thermoelectric figures of merit. The Na1 xPbmSbyTem+2 materials could find applications in devices for power generation from a wide variety of hot sources, for example, vehicle exhausts, coal-burning installations, or electric power utilities. Na1 xPbmSbyTem+2 (y 1) samples (see Supporting Information for synthesis details) exhibit p-type conduction from 300 to 700 K. Ingots with the composition Na0.95Pb19SbTe21 (m= 19, x= 0.05, y= 1) exhibit an electrical conductivity of s= 1422 Scm 1 with a positive thermopower of S= 105 mVK 1 at room temperature. This leads to the relatively high power factor of PF= 15.6 mWcm K . The temperature dependence of the electrical conductivity and the thermopower of Na0.95Pb19SbTe21 are shown in Figure 1A. The conductivity decreases with increasing temperature, which is consistent with degenerate semiconductors, and reaches s= 150 Scm 1 at 700 K. However, the thermopower increases rapidly to S= 357.6 mVK 1 at 700 K, yielding a much higher power factor of PF= 19 mWcm K . For samples of composition Na0.95Pb20SbTe22 (m= 20, x= 0.05, y= 1), an electrical conductivity of s= 1541 Scm 1 and a [*] Dr. P. F. P. Poudeu, Prof. M. G. Kanatzidis Department of Chemistry Michigan State University East Lansing, MI 48824 (USA) Fax: (+1)517-353-1793 E-mail: kanatzid@cem.msu.edu
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