Zintl phase Mg3Sb2 is a promising thermoelectric material in medium to high temperature range due to its low band gap energy and characteristic electron-crystal phonon-glass behavior. P-type Mg3Sb2 has conventionally exhibited lower thermoelectric properties compared to its n-type counterparts, which have poor electrical conductivity. To address these problems, a small amount of Sn doping was considered in this alloy system. P-type Mg3Sb2 was synthesized by controlled melting, pulverizing, and subsequent vacuum hot pressing (VHP) method. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to investigate phases and microstructure development during the process. Single phase Mg3Sb2 was successfully formed when 16 at.% of Mg was excessively added to the system. Nominal compositions of Mg3.8Sb2-xSnx (0 ≤ x ≤ 0.008) were considered in this study. Thermoelectric properties were evaluated in terms of Seebeck coefficient, electrical conductivity, and thermal conductivity. A peak ZT value ≈ 0.32 was found for the specimen Mg3.8Sb1.994Sn0.006 at 873 K, showing an improved ZT value compared to intrinsic one. Transport properties were also evaluated and discussed.

In this work, the effects of hydrogen reduction on the microstructure and thermoelectric properties of (GeTe)0.85(AgSbTe2)0.15 (TAGS-85) were studied by a combination of gas atomization and spark plasma sintering. The crystal structure and microstructure of TAGS-85 were characterized by X-ray diffraction(XRD) and scanning electron microscopy (SEM). The oxygen content of both powders and bulk samples were found to decrease with increasing reduction temperature. The grain size gradually increased with increasing reduction temperature due to adhesion of fine grains in a temperature range of 350 to 450 °C. The electrical resistivity was found to increase with reduction temperature due to a decrease in carrier concentration. The Seebeck coefficient decreased with increasing reduction temperature and was in good agreement with the carrier concentration and carrier mobility. The maximum power factor, 3.3 × 10−3 W/mK2, was measured for the non-reduction bulk TAGS-85 at 450 °C.

P-type ternary Bi0.5Sb1.5Te3 alloys are fabricated via mechanical alloying (MA) and spark plasma sintering (SPS). Different ball sizes are used in the MA process, and their effect on the microstructure; hardness, and thermoelectric properties of the p-type BiSbTe alloys are investigated. The phases of milled powders and bulks are identified using an X-ray diffraction technique. The morphology of milled powders and fracture surface of compacted samples are examined using scanning electron microscopy. The morphology, phase, and grain structures of the samples are not altered by the use of different ball sizes in the MA process. Measurements of the thermoelectric (TE) transport properties including the electrical conductivity, Seebeck coefficient, and power factor are measured at temperatures of 300- 400 K for samples treated by SPS. The TE properties do not depend on the ball size used in the MA process.

Bismuth antimony telluride (BiSbTe) thermoelectric materials were successfully prepared by a spark plasma sintering process. Crystalline BiSbTe ingots were crushed into small pieces and then attrition milled into fine powders of about 300 nm ~ 2μm size under argon gas. Spark plasma sintering was applied on the BiSbTe powders at 240, 320, and 380˚C, respectively, under a pressure of 40 MPa in vacuum. The heating rate was 50˚C/min and the holding time at the sintering temperature was 10 min. At all sintering temperatures, high density bulk BiSbTe was successfully obtained. The XRD patterns verify that all samples were well matched with the Bi0.5Sb1.5Te3. Seebeck coefficient (S), electric conductivity (σ) and thermal conductivity (k) were evaluated in a temperature range of 25~300˚C. The thermoelectric properties of BiSbTe were evaluated by the thermoelectric figure of merit, ZT (ZT = S2σT/k). The grain size and electric conductivity of sintered BiSbTe increased as the sintering temperature increased but the thermal conductivity was similar at all sintering temperatures. Grain growth reduced the carrier concentration, because grain growth reduced the grain boundaries, which serve as acceptors. Meanwhile, the carrier mobility was greatly increased and the electric conductivity was also improved. Consequentially, the grains grew with increasing sintering temperature and the figure of merit was improved.

Bismuth-telluride based thermoelectric powders were fabricated by two-step planetary milling process which produces bimodal size distribution ranging . The powders were reduced in hydrogen atmosphere to minimize oxygen contents which cause degradation of thermoelectric performance by decreasing electrical conductivity. Oxygen contents were decreased from 0.48% to 0.25% by the reduction process. In this study, both the as-synthesized and the reduced powders were consolidated by the spark plasma sintering process at for 10 min at the heating rate of and then their thermoelectric properties were investigated. The sintered samples using the reduced p-type thermoelectric powders show 15% lower specific electrical resistivity () than those of the as-synthesized powders while Seebeck coefficient and thermal conductivity do not change a lot. The results confirmed that ZT value of thermoelectric performance at room temperature was improved by 15% due to high electric conductivity caused by the controlled oxygen contents present at bismuth telluride materials.

Fe doped skutterudite CoSb3 with a nominal composition of FexCo1-xSb12 (0≤x≤2.5) have been synthesized by mechanical alloying (MA) of elemental powders, followed by vacuum hot pressing. Phase transformations during mechanical alloying and vacuum hot pressing were systematically investigated using XRD. Single phase skutterudite was successfully produced by vacuum hot pressing using as-milled powders without subsequent annealing. However, second phase of FeSb2 was found to exist in case of x≥2, suggesting the solubility limit of Fe with Co in this system. Thermoelectric properties as functions of temperature and Fe contents were evaluated for the hot pressed specimens. Fe doping up to x=1.5 with Co in FexCo4-xSb12 appeared to increase thermoelectric figure of merit (ZT) and the maximum ZT was found to be 0.78 at 525K in this study.

계 열전반도체 재료는 200 ~ 400K 정도의 저온에서 에너지 변환 효율이 가장 높은 재료로서 열전냉각 및 발전재료로 제조볍 및 특성에 관한 많은 연구가 진행되어 왔다. 전자냉각 모듈의 제조에는 P형 및 N형 계 단결정이 주로 사용되고 있으나. 단결정은 C축에 수직한 벽개면을 따라 균열이 쉽게 전파하기 때문에 소자 가공사 수윤 저하가 가장 큰 문제점으로 지적되고 있다. 이에 따라 최근 열전재료의 가공방법에 따른 회수율 증가 및 열전특성 향상에 관한