Giri Joshi

Enhanced Thermoelectric Figure-of-Merit in Nanostructured p-type Silicon Germanium Bulk Alloys

A dimensionless thermoelectric figure-of-merit (ZT) of 0.95 in p-type nanostructured bulk silicon germanium (SiGe) alloys is achieved, which is about 90% higher than what is currently used in space flight missions, and 50% higher than the reported record in p-type SiGe alloys. These nanostructured bulk materials were made by using a direct current-induced hot press of mechanically alloyed nanopowders that were initially synthesized by ball milling of commercial grade Si and Ge chunks with boron powder. The enhancement of ZT is due to a large reduction of thermal conductivity caused by the increased phonon scattering at the grain boundaries of the nanostructures combined with an increased power factor at high temperatures.

Enhanced thermoelectric figure of merit in nanostructured n-type silicon germanium bulk alloy

The dimensionless thermoelectric figure of merit (ZT) of the n-type silicon germanium (SiGe) bulk alloy at high temperature has remained at about one for a few decades. Here we report that by using a nanostructure approach, a peak ZT of about 1.3 at 900 °C in an n-type nanostructured SiGe bulk alloy has been achieved. The enhancement of ZT comes mainly from a significant reduction in the thermal conductivity caused by the enhanced phonon scattering off the increased density of nanograin boundaries. The enhanced ZT will make such materials attractive in many applications such as solar, thermal, and waste heat conversion into electricity.

Experimental Studies on Anisotropic Thermoelectric Properties and Structures of n-Type Bi2Te2.7Se0.3

The peak dimensionless thermoelectric figure-of-merit (ZT) of Bi(2)Te(3)-based n-type single crystals is about 0.85 in the ab plane at room temperature, which has not been improved over the last 50 years due to the high thermal conductivity of 1.65 W m(-1) K(-1) even though the power factor is 47 x 10(-4) W m(-1) K(-2). In samples with random grain orientations, we found that the thermal conductivity can be decreased by making grain size smaller through ball milling and hot pressing, but the power factor decreased with a similar percentage, resulting in no gain in ZT. Reorienting the ab planes of the small crystals by repressing the as-pressed samples enhanced the peak ZT from 0.85 to 1.04 at about 125 degrees C, a 22% improvement, mainly due to the more increase on power factor than on thermal conductivity. Further improvement is expected when the ab plane of most of the small crystals is reoriented to the direction perpendicular to the press direction and grains are made even smaller.

Power Factor Enhancement by Modulation Doping in Bulk Nanocomposites

We introduce the concept of modulation doping in three-dimensional nanostructured bulk materials to increase the thermoelectric figure of merit. Modulation-doped samples are made of two types of nanograins (a two-phase composite), where dopants are incorporated only into one type. By band engineering, charge carriers could be separated from their parent grains and moved into undoped grains, which would result in enhanced mobility of the carriers in comparison to uniform doping due to a reduction of ionized impurity scattering. The electrical conductivity of the two-phase composite can exceed that of the individual components, leading to a higher power factor. We here demonstrate the concept via experiment using composites made of doped silicon nanograins and intrinsic silicon germanium grains.

Enhanced Thermoelectric Figure of Merit of p-Type Half-Heuslers

Half-Heuslers would be important thermoelectric materials due to their high temperature stability and abundance if their dimensionless thermoelectric figure of merit (ZT) could be made high enough. The highest peak ZT of a p-type half-Heusler has been so far reported about 0.5 due to the high thermal conductivity. Through a nanocomposite approach using ball milling and hot pressing, we have achieved a peak ZT of 0.8 at 700 °C, which is about 60% higher than the best reported 0.5 and might be good enough for consideration for waste heat recovery in car exhaust systems. The improvement comes from a simultaneous increase in Seebeck coefficient and a significant decrease in thermal conductivity due to nanostructures. The samples were made by first forming alloyed ingots using arc melting and then creating nanopowders by ball milling the ingots and finally obtaining dense bulk by hot pressing. Further improvement in ZT is expected when average grain sizes are made smaller than 100 nm.

Theoretical studies on the thermoelectric figure of merit of nanograined bulk silicon

In this paper, we investigate the phonon transport in silicon nanocomposites using Monte Carlo simulations considering frequency-dependent phonon mean free paths, and combine the phonon modeling with electron modeling to predict the thermoelectric figure of merit (ZT) of silicon nanocomposites. The model shows that while grain interface scattering of phonons is negligible for large grain sizes around 200 nm, ZT can reach 1.0 at 1173 K if the grain size can be reduced to 10 nm. Our results show the potential of obtaining a high ZT in bulk silicon by the nanocomposite approach.

Understanding of the contact of nanostructured thermoelectric n-type Bi2Te2.7Se0.3 legs for power generation applications

Traditional processes of making contacts (metallization layer) onto bulk crystalline Bi2Te3-based materials do not work for nanostructured thermoelectric materials either because of weak bonding strength or an unstable contact interface at temperatures higher than 200 °C. Hot pressing of nickel contact onto nanostructured thermoelectric legs in a one-step process leads to strong bonding. However, such a process results in large contact resistance in n-type Ni/Bi2Te2.7Se0.3/Ni legs, although not in p-type Ni/Bi0.4Sb1.6Te3/Ni legs. A systematic study was carried out to investigate the detailed reaction and diffusion at the interface of the nickel layer and n-type Bi2Te3-based thermoelectric material layer. We found that a p-type region formed within the n-type Bi2Te2.7Se0.3 during hot pressing due to Te deficiency and Ni doping, leading to a large contact resistance.

Experimental determination of the Lorenz number in Cu0.01Bi2Te2.7Se0.3 and Bi0.88Sb0.12

Nanostructuring has been shown to be an effective approach to reduce the lattice thermal conductivity and improve the thermoelectric figure of merit. Because the experimentally measured thermal conductivity includes contributions from both carriers and phonons, separating out the phonon contribution has been difficult and is mostly based on estimating the electronic contributions using the Wiedemann-Franz law. In this paper, an experimental method to directly measure electronic contributions to the thermal conductivity is presented and applied to Cu 0.01Bi2Te2.7Se0.3 ,[ Cu0.01Bi2Te2.7Se0.3]0.98Ni0.02 ,a nd Bi 0.88Sb0.12. By measuring the thermal conductivity under magnetic field, electronic contributions to thermal conductivity can be extracted, leading to knowledge of the Lorenz number in thermoelectric materials.

NANOCOMPOSITES TO ENHANCE ZT IN THERMOELECTRICS

The concept of using “self-assembled” and “force-engineered” nanostructures to enhance the thermoelectric figure of merit relative to bulk homogeneous and composite materials is presented in general terms. Specific application is made to the Si-Ge system for use in power generation at high temperature. The scientific advantages of the nanocomposite approach for the simultaneous increase in the power factor and decrease of the thermal conductivity are emphasized along with the practical advantages of having bulk samples for property measurements and a straightforward path to scale-up materials synthesis and integration of nanostructured materials into thermoelectric cooling and power generation devices.

A quick and efficient measurement technique for performance evaluation of thermoelectric materials

Evaluating the performance of thermoelectric (TE) materials is critical for developing an efficient long lasting thermoelectric generator. Various parameters like resistance, TE power, TE efficiency as a function of temperature and time play an important role in developing and optimizing TE materials and legs. If one needs to evaluate the TE legs for performance or contact metallization optimization, study of a brazed or packaged device everytime could prove to be an expensive, time consuming process especially as a quick intermediate qualification. In this work, a simple approach that uses eutectic Gallium Indium (Ga–In) paste as a metallizing substitute with good electrical/thermal contact is employed which also avoids the need for brazing/welding (or any permanent joining) and provides a reliable platform for a quick leg qualification. Using open circuit voltage (V oc) and device voltage (V d), one can evaluate important TE quantities like peak power, material resistance changes, peak current and power versus current characteristics to understand the leg performance. The proposed approach is successfully demonstrated with three different TE material systems namely Bismuth Telluride, Skutterudite and Half Heusler systems.