Engineering topics
Publications and source records attributed to Borshchevsky, Alexander.
A thermoelectric device formed of nanowires on the nm scale. The nanowires are preferably of a size that causes quantum confinement effects within the wires. The wires are connected together into a bundle to increase the power density.
The present invention is embodied in high performance p-type thermoelectric materials having enhanced thermoelectric properties and the methods of preparing such materials. In one aspect of the invention, p-type semiconductors of formula Zn4-xAxSb3-yBy wherein 0?x?4, A is a transition metal, B is a pnicogen, and 0?y?3 are formed for use in manufacturing thermoelectric devices with substantially enhanced operating characteristics and improved efficiency. Two methods of preparing p-type Zn4Sb3 and related alloys of the present invention include a crystal growth method and a powder metallurgy method.
Nanowire thermoelectric devices, now under development, are intended to take miniaturization a step beyond the prior state of the art to exploit the potential advantages afforded by shrinking some device features to approximately molecular dimensions (of the order of 10 nm). The development of nanowire-based thermoelectric devices could lead to novel power-generating, cooling, and sensing devices that operate at relatively low currents and high voltages. Recent work on the theory of thermoelectric devices has led to the expectation that the performance of such a device could be enhanced if the diameter of the wires could be reduced to a point where quantum confinement effects increase charge-carrier mobility (thereby increasing the Seebeck coefficient) and reduce thermal conductivity. In addition, even in the absence of these effects, the large aspect ratios (length of the order of tens of microns diameter of the order of tens of nanometers) of nanowires would be conducive to the maintenance of large temperature differences at small heat fluxes. The predicted net effect of reducing diameters to the order of tens of nanometers would be to increase its efficiency by a factor of .3. Nanowires made of thermoelectric materials and devices that comprise arrays of such nanowires can be fabricated by electrochemical growth of the thermoelectric materials in templates that contain suitably dimensioned pores (10 to 100 nm in diameter and 1 to 100 microns long). The nanowires can then be contacted in bundles to form devices that look similar to conventional thermoelectric devices, except that a production version may contain nearly a billion elements (wires) per square centimeter, instead of fewer than a hundred as in a conventional bulk thermoelectric device or fewer than 100,000 as in a microdevice. It is not yet possible to form contacts with individual nanowires. Therefore, in fabricating a nanowire thermoelectric device, one forms contacts on nanowires in bundles of the order of 10-microns wide. The fill factor for the cross-section of a typical bundle is about 1/2. Nanowires have been grown in alumina templates with pore diameters of 100 and 40 nm.
The present invention is embodied in high performance p-type thermoelectric materials having enhanced thermoelectric properties and the methods of preparing such materials. In one aspect of the invention, p-type semiconductors of formula Zn.sub.4-x A.sub.x Sb.sub.3-y B.sub.y wherein 0.ltoreq.x.ltoreq.4, A is a transition metal, B is a pnicogen, and 0.ltoreq.y.ltoreq.3 are formed for use in manufacturing thermoelectric devices with substantially enhanced operating characteristics and improved efficiency. Two methods of preparing p-type Zn.sub.4 Sb.sub.3 and related alloys of the present invention include a crystal growth method and a powder metallurgy method.
Transition metals of Group VIII (Co, Rh and Ir) have been prepared as semiconductor compounds with the general formula TSb.sub.3. The skutterudite-type crystal lattice structure of these semiconductor compounds and their enhanced thermoelectric properties results in semiconductor materials which may be used in the fabrication of thermoelectric elements to substantially improve the efficiency of the resulting thermoelectric device. Semiconductor materials having the desired skutterudite-type crystal lattice structure may be prepared in accordance with the present invention by using vertical gradient freezing techniques and/or liquid phase sintering techniques. Measurements of electrical and thermal transport properties of selected semiconductor materials prepared in accordance with the present invention, demonstrated high Hall mobilities (up to 1200 cm.sup.2.V.sup.-1.s.sup.-1) and good Seebeck coefficients (up to 150 .mu.VK.sup.-1 between 300.degree. C. and 700.degree. C.). Optimizing the transport properties of semiconductor materials prepared from elemental mixtures Co, Rh, Ir and Sb resulted in a substantial increase in the thermoelectric figure of merit (ZT) at temperatures as high as 400.degree. C. for thermoelectric elements fabricated from such semiconductor materials.
New skutterudite phases including Ru.sub.0.5 Pd.sub.0.5 Sb.sub.3, RuSb.sub.2 Te, and FeSb.sub.2 Te, have been prepared having desirable thermoelectric properties. In addition, a novel thermoelectric device has been prepared using skutterudite phase Fe.sub.0.5 Ni.sub.0.5 Sb.sub.3. The skutterudite-type crystal lattice structure of these semiconductor compounds and their enhanced thermoelectric properties results in semiconductor materials which may be used in the fabrication of thermoelectric elements to substantially improve the efficiency of the resulting thermoelectric device. Semiconductor materials having the desired skutterudite-type crystal lattice structure may be prepared in accordance with the present invention by using powder metallurgy techniques. Measurements of electrical and thermal transport properties of selected semiconductor materials prepared in accordance with the present invention, demonstrated high Hall mobilities and good Seebeck coefficients. These materials have low thermal conductivity and relatively low electrical resistivity, and are good candidates for low temperature thermoelectric applications.
Transition metals (T) of Group VIII (Co, Rh and Ir) have been prepared as semiconductor alloys with Sb having the general formula TSb.sub.3. The skutterudite-type crystal lattice structure of these semiconductor alloys and their enhanced thermoelectric properties results in semiconductor materials which may be used in the fabrication of thermoelectric elements to substantially improve the efficiency of the resulting thermoelectric device. Semiconductor alloys having the desired skutterudite-type crystal lattice structure may be prepared in accordance with the present invention by using vertical gradient freeze techniques, liquid-solid phase sintering techniques, low temperature powder sintering and/or hot-pressing. Measurements of electrical and thermal transport properties of selected semiconductor materials prepared in accordance with the present invention, demonstrated high Hall mobilities (up to 8000 cm.sup.2.V.sup.-1.s.sup.-1), good Seebeck coefficients (up to 400 .mu.VK.sup.-1 between 300.degree. C. and 700.degree. C.), and low thermal conductivities (as low as 15 mW/cmK). Optimizing the transport properties of semiconductor materials prepared from elemental mixtures Co, Rh, Ir and Sb resulted in a two fold increase in the thermoelectric figure of merit (ZT) at temperatures as high as 400.degree. C. for thermoelectric elements fabricated from such semiconductor materials.
New semiconducting materials with p-type carrier mobility values much higher than state-of-art semiconductors discovered. Nine compounds, antimonides CoSb(sub3), RhSb(sub3), IrSb(sub3), arsenides CoAs(sub3), RhAs(sub3), IrAs(sub3), and phosphides CoP(sub3), RhP(sub3) and IrP(sub3), exhibit same skutterudite crystallographic structure and form solid solutions of general composition Co(1-x-y)RH(x)Ir(y)P(1-w-z)As(w)Sb(z). Materials exhibit high hole mobilities, high doping levels, and high electronic figures of merit. Some compositions show great potential for application to thermoelectric devices.
Report discusses preparation of thermoelectric materials from melts. First stage in preparation of thermoelectric material is one of alloying or synthesis, in which high-purity elemental constituents melted together in stoichiometric or nonstoichiometric mixture.
Figures of merit almost double current state-of-art thermoelectric materials. IrSb3 is semiconductor found to exhibit exceptional thermoelectric properties. CoSb3 and RhSb3 have same skutterudite crystallographic structure as IrSb3, and exhibit exceptional transport properties expected to contribute to high thermoelectric performance. These three compounds form solid solutions. Combination of properties offers potential for development of new high-performance thermoelectric materials for more efficient thermoelectric power generators, coolers, and detectors.
Ir(1-x-y)Rh(x)Co(y)Sb(3) semiconductors synthesized by gradient-freeze and sintering techniques. Sintering techniques used for variety of compositions; gradient-freeze technique used for RhSb(3) and CoSb(3).
Report discusses design of proposed radioisotope thermoelectric generators, each of which produces about 30 mW of electric power for decades, fits in package about the size of D cell, and would have mass of only 70 g.