Thermal Conductivity Reduction in p-type Si80Ge20 Alloys due to Ultrafine BN Particulates
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Publications and source records attributed to Fleurial, Jean-Pierre.
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Transport properties of large single crystalline samples of Ru_2Ge_3 grown from the melt have been investigated in a 25-1000 C temperature range. A diffusionless transition between 500 and 550C from a high temperature tetragonal structure to a low temperature orthorhombic structure was clearly observed. Results showed that both the low temperature orthorhombic and the high temperature structural tetragonal phase are semiconductors. Some anisotropy of the transport coefficients was determined by measuring the samples in orientations parallel and perpendicular to the preferential direction of crystal growth. Large Seebeck coefficient (up to 400 microVK^(-1)) and low thermal conductivity (as low as 20x10^(-3) Wcm^(-1)K^(-1)) were achieved for the low temperature orthorhombic phase. Difficulties in preparing heavily doped samples and low Hall mobilities have limited values for the maximum figure of merit to 0.5 x 10^(-3) K^(-1) at 500 C.
The addition of ultrafine scattering centers into Bi_2Te_3-based materials and their impact on the thermal and electrical transport properties in a 200-500 K temperature range are discussed. Based on previous theoretical efforts, the resulting improvements in the figure of merit of these heavily doped thermoelectric semiconductors were calculated as a function of composition, temperature, doping level, particulate size and concentration. Determination of the lattice thermal conductivity of the various alloys was conducted by considering phonon-phonon, carrier-phonon, point defect and inert scattering center scattering mechanisms. Degradation of the electrical properties due to the increase scattering rate was also taken into account. Practical application of these results is considered.
A comprehensive experimental and theoretical work has been conducted in order to optimize the thermoelectric properties of Si_(80)Ge_(20) materials and reach the goal of a combined figure of merit value of 0.85x10^(-3) K^(-1) averaged over a 600-1000 C temperature range. Improvement for the n-type material has been obtained by determining the optimum amounts of gallium and phosphorus dopants necessary to achieve optimum carrier mobility and concentration. The emphasis is now on the consistent reproducibility of these results through understanding and control of the hot-pressing parameters relating microstructure and composition to the transport properties. The optimum doping level has now been firmly established for p-type materials, and work is concentrating on the reduction in thermal conductivity. BN ultra fine particles have been successfully incorporated into fully dense samples and have resulted in desired improvement of the figure of merit...
Electrical measurements made by four point probes, two of which double as temperature probes. Laboratory apparatus measures both Seebeck coefficients and electrical resistivities of candidate thermoelectric materials at temperatures from ambient to 1,300 K. Apparatus makes possible to take both measurements alternately and in rapid succession during same heating cycle, thereby reducing distortion.
The effect of changes in the carrier concentration and mobility for heavily doped n-type SiGe on the electrical power factor has been investigated. It has been shown that power factors of 37-40 microV/cm-K-squared can be achieved with carrier concentrations of 2.0 - 2.5 x 10 exp 20/cu cm and mobilities of 38-40 sq cm/V-sec. Many samples with suitable carrier concentration do not have high mobilities and some rationale for this behavior is presented. Initial results are presented on fabrication of n-type samples from ultrafine powders. The emphasis in this work is to achieve thermal conductivity reductions by adding inert particles to scatter midfrequency phonons.
Spark erosion was used to produce ultra-fine particles of SiGe thermoelectric material and boron nitride, an inert phonon-scattering material. A homogeneous powder was made by mixing the two powders. The mixture was hot pressed to produce a thermoelectric material with uniformity dispersed, ultra-fine, inert, phonon-scattering centers. It is shown that, in samples with inert boron nitride or silicon nitride, thermal conductivity of a SiGe alloy can be reduced by about 25 percent while maintaining the electrical properties of the samples. Annealing of all the samples at 1525 K caused grain growth to over a micron, eliminating the detrimental effect attributable to small grains. Only in the sample with boron nitride the thermal conductivity did remain well below that for standard p-type SiGe (about 25 percent), while the electrical resistivity and Seebeck coefficient were very close to the values for standard p-type 80/20 SiGe.
Although important efforts are actually devoted to improve Si-Ge materials, their thermoelectric energy conversion efficiency remains relatively low and the nondimensional ZT value does not exceed 1. Higher values can be obtained by investigating new materials. A search for new high temperature thermoelectric materials identified a certain number of compounds between transition metals and bismuth, antimony and germanium as potential candidates. Results of the preliminary synthesis of samples by a variety of techniques (Bridgman, mechanical alloying) are presented as well as some electrical measurements. Some compounds showed interesting properties and need to be investigated in more details.
Experimental and theoretical work has been conducted at the Jet Propulsion Laboratory to improve the thermoelectric properties of n-type SiGe materials. Particular emphasis has been placed upon the understanding of the differences in dopant solid solubilities when multidoping with both Ga and P instead of P alone, as in standard SiGe alloys. A set of various experimental techniques for obtaining heavily doped hot-pressed samples coupled with thermodynamic theoretical considerations was used to relate microstructure and composition to electrical and thermal transport properties. Application of these results to high-temperature heat treatments of several SiGe/GaP samples achieved substantial improvements of the thermoelectric figure of merit Z, with average values close to 1 x 10-3K-1 over the 600-1000 C temperature range. A set of systematic anneals on heavily doped SiGe/GaP materials is reported in an attempt to consistently reproduce the optimized thermoelectric properties.
Improvements to the figure-of-merit of n-type SiGe have been achieved via a systematic anneal study aimed at determining the optimal P:Ga ratio. Figures-of-merit of 0.85 to 0.90 x 10-3K-1 have been routinely and reproducibly achieved starting with an initial P:Ga ratio of 3:1. These samples have carrier concentrations in excess of 4.0 x 1020/cu cm, the highest reported for SiGe. This value has been shown to be too high, resulting in unfavorably low Seebeck coefficients. The optimal carrier concentration has been shown to be 1.5-3.0 x 1020/cu cm. Thus, further improvements will be achieved by reductions in the P and Ga concentrations.
Efforts to improve the thermoelectric efficiency of silicon-germanium alloys are discussed. These efforts are essentially focused on substantially enhancing carrier concentration levels and thus increasing the power factor values of n-type materials. With the help of thermodynamic phase diagram calculations, a combination of various crystal growth and dopant saturation techniques is used for this purpose. Bulk polycrystal growth of double-doped materials is achieved by zone leveling while a new method (the traveling heater method) for high-quality single-crystal growth of SiGe is being developed. Thin films of homogeneous single-crystalline multidoped Si80Ge20 have also been successfully grown from low-temperature melts to investigate combined dopant solid solubility variations. Very high carrier concentration levels were obtained by (P+As)-combined diffusion in zone-leveled and hot-pressed materials. The good overall understanding of doping mechanisms which has been achieved should enable optimization of the thermoelectric properties over this extended carrier concentration range. Reductions in thermal conductivity are being sought by introduction of very small phonon scattering centers (inert material) in the initial powders-precursors of Si-Ge alloys. This approach should benefit both n- and p-type materials.
It is shown that heavy doping of n-type Si/Ge alloys with phosphorus and arsenic (V-V doping interaction) by diffusion leads to a significant enhancement of their carrier concentration and possible improvement of the thermoelectric figure of merit. High carrier concentrations were achieved by arsenic doping alone, but for a same doping level higher carrier mobilities and lower resistivities are obtained through phosphorus doping. By combining the two dopants with the proper diffusion treatments, it was possible to optimize the different properties, obtaining high carrier concentration, good carrier mobility and low electrical resistivity. Similar experiments, using the III-V doping interaction, were conducted on boron-doped p-type samples and showed the possibility of overcompensating the samples by diffusing arsenic, in order to get n-type behavior.