Climate change is a subject of deep distress in today’s world. Over dependence on hydrocarbon has resulted in serious environmental problems. Rising sea level, global warming and ozone layer depletion are the mainstream of any discuss world over. The collective goal of cutting carbon emission by the year 2020has prompted the search for clean, alternative energy sources. This effort are already yielding good reward as other forms of energy such as solar, wind, nuclear and hydro have received huge investment and renew interest over the past decade. Thermoelectric materials over the past decades have been tipped to replace conventional means of power generations as these materials have the ability to convert heat to electrical energy and vice versa. They are simple, have no moving parts and use no greenhouse gases. But the major drawback of these materials is their low conversion efficiency. Hence there is a need to enhance the efficiency of thermoelectric material to fulfill their undeniable potentials. A parameter called the thermoelectric figure of merit, ZT defines the efficiency of a thermoelectric material. ZT relates three non-mutually exclusive transport properties namely Seebeck coefficient, electrical conductivity and thermal conductivity. Efficient thermoelectric material should possess high Seebeck coefficient, high electrical conductivity and low thermal conductivity. Hence, one of the interesting ideas in the area of thermoelectric research is the concept of designing a bulk material with high density of phonon scattering centers so has to reduce the lattice contribution to thermal conductivity but at the same time have minimum impact oncharge carriers. This is usually achieved by utilizing interphase and grain boundaries which are localized defects to scatter phonons. The volume fraction of the grain/interphase boundaries can be control through phase modification and microstructure design. This thesis is centered on Bi-Sb-Te systems which are the present room temperature state of the earth thermoelectric material. The investigation revolves around developing a new kind of microstructure in the well-studied Bi-Sb-Te system that shows tremendous potential as a means to reduce lattice contribution to thermal conductivity. The idea of having both p and n-type thermoelectric material preferably from the same material was also a motivation in our investigation. The thesis isdivided into six chapters. The first chapter introduces the concept of thermoelectricity i.e. the direct conversion of thermal energy into electricity. The physics involved and contribution of individual to the science of thermoelectricity were enumerated. Efficiency, optimization and material selection for better thermoelectric performance were briefly enumerated. Prospective materials that are currently been investigated for better thermoelectric properties were also mentioned. The structure of the Bi-Sb-Te system which is the focus of this thesis is present in this chapter including doping effect on the thermoelectric performance of the system as well as the various methods present been employed to improve the thermoelectric properties of the system. Finally the chapter enumerates the scope and object of the present thesis. The different experimental procedures adopted in the present thesis arediscussed in chapter 2. The details of different processing routes followed to synthesize flame-melted ingots, flame-melted + low temperature milled (cryo milling) + spark plasma sintering (SPS) alloy and flame-melted + melt spinning + spark plasma sintering (SPS) alloy, are discussed followed by the various structural and functional characterization techniques. The unique advantage of the spark plasma sintering techniques over the conventional sintering method was talked out in detail. The structural characterizations performed on the synthesized alloys include XRD, SEM and whilethe functional characterizations comprised of Hall measurement, Seebeck coefficient, electrical resistivity and thermal conductivity measurements. Thermoelectric properties of selected composition of Bi-Sb-Te synthesized via flame-melting are presented in chapter 3.Detail study of four analyzed compositions namelyBi24Sb20Te56, Bi20Sb12Te69, Bi16Sb5Te79 and Bi29Sb11Te60resulted in four unique microstructure and different volume fraction of primary and secondary phases. The resultant morphologies of the microstructure were observed to have influence the thermoelectric behavior corresponding to each composition. The sole influence of anti-structural defects on the conductivity type and the role of microstructure morphologies and length scale were understood in this chapter. Samples with segregated Te and a solid solution BiSbTe3(eutectic morphology) form an n-type thermoelectric material while samples with only solid solution BiSbTe3 forms a p-type thermoelectric material. Pair of n-type and p-type material was obtained without the introduction of external dopant.The pair shows good compatibility factorsuitable for thermoelectric device. In chapter 4, the thermoelectric properties of four selected composition of Bi-Sb-Te synthesized via low temperature milling plus spark plasma sintering is addressed. The analyzed compositions are as follows Bi24Sb20Te56, Bi18Sb11Te71, Bi17Sb6Te77, and Bi28Sb15Te57 respectively. The effect of low temperature milling combine with the prospect of minimum grain growth of spark plasma sintering on the thermoelectric properties of the selected compositions were determined. Samples with eutectic morphology which would otherwise scatter charge carriers were observed to have the highest carrier mobility as a result of high volume fraction of Te phase which serves as a donor injecting excess electrons into the system. The impact of small grain size was observed on the transport properties of the sample Bi28Sb15Te57 with the highest electrical resistivity, the best Seebeck coefficient and the lowest thermal conductivity. Pair of n-type and p-type material was obtained without the introduction of external doping elements. The pairshows good compatibility factor suitable for segmented thermoelectric device. Chapter 5 narrates the thermoelectric properties of four compositions namely Bi30Sb13Te58, Bi23Sb13Te65, Bi18Sb5Te77 and Bi23Sb20Te58subjected to melt spinning plus spark plasma sintering.High cooling rate obtained during melt spinning process was observed in this chapter to cause a shift of composition which resulted in a microstructure morphology with eutectic colonies that is predominantly Te rich. These Te rich colonies in the sample Bi30Sb13Te58 was observed to change the conductivity type of the sample from an otherwise p-type to n-type while also aiding bipolar conduction which was detrimental to the overall thermoelectric performance of the alloy. Segregated Te in the form of eutectic morphology helps to inject excess electron into the bulk of the sample Bi23Sb13Te65 and Bi18Sb5Te77hereby increases the observed electrical conductivity which by virtue of the microstructure morphology is expected to be low. As a result of the processing routes, all four compositions in this chapter shown-type conductivity. Chapter 6 presents the summary of the important conclusions drawn from this work.

找尋新穎的熱電材料是現在許多物理、化學以及材料學家的熱門研究，熱電材料的益處在於可將生活中所產生的廢熱轉化成電能再度利用，可應用在於熱機或是冷凍機之上。 首先，在第一個研究之中，透過布理奇曼法在1050 ℃之下維持10個小時用以製作Cu0.01Bi2Te2.7Se0.3塊材，以及透過水熱法製造出Cu0.01Bi2Te2.7Se0.3奈米粒子，並且將兩種不同尺寸的粒子做不同比例的混合：奈米粒子(粒徑：20~100奈米)重量百分比0、10、20、30和100；接著探討火花電漿燒結法及奈米聚合物對熱電性質之影響。在實驗中發現材料中混入百分之三十的奈米粒子可提升熱電優質係數約一倍，由0.35提升至0.74。若是可以將起初塊材的熱電優質係數提升至較良好的0.7以上，再透過奈米聚合和燒結，其熱電係數在400 K左右是可以超過1的。由這個研究顯示出：火花電漿燒結以及奈米聚合是可以有效的提升熱電優質係數，其主要原因來自於成功的降低熱傳導係數並同時維持住原本所擁有的電阻率以及席貝克係數的提升，而熱傳導降低因於樣品中的奈米結構所造成的粒子邊界增加、晶格的不匹配導致抑制聲子的傳熱所形成的結果。 第二個研究為一樣是透過布理奇曼法在750 ℃之下維持12個小時用以製作BixSb2-xTe3塊材，其中x分別為0.4、0.45、0.5以及0.6，本實驗主要為探討Bi的量對於BiSbTe所造成的影響。由結果中顯示x高於0.5和低於0.5所呈現的熱傳性質的趨勢有些許不同。在x為0.45的塊材中，得到本實驗中在室溫之下，最佳的熱電優質係數1.5，獲得此結果的主要原因來自於相對較低的電阻率，並可觀察到x為0.45的載子濃度高於0.4、0.5和0.6的結果，其將可以佐證x=0.45塊材的低電組率所造成的優質係數提升。 / Physicists, chemists and material scientists at many major universities and research institutions throughout the world are attempting to create novel materials with high thermoelectric (TE) efficiency. It will be beneficial to harvest waste heat into electrical energy. Specialty heating and cooling are other major applications for this class of new TE materials. In the first study, bulk and nanoparticles of Cu0.01Bi2Te2.7Se0.3 were prepared separately. The Cu0.01Bi2Te2.7Se0.3 bulk was fabricated by Bridgeman method at 1050 ℃ for 10 hrs and the nanoparticles were made through hydrothermal method. Two kinds of powders were mixed with the ratios of NPs 0, 10, 20, 30 and 100 wt% and sintered by the SPS technique to form the composite specimens. The ZT value can be enhanced over 100% from 0.35 to 0.74 for specimen with 30 wt% nanoparticles. The consequence indicates that the SPS process and mixing nanocomposite can effectively enhance ZT value. The enhancements were caused mainly by the presence of nanostructured regions existing within the samples which lowered the thermal conductivity. The phenomenon is due to the presence of significant number of grain boundaries, shorten phonon mean free path and lattice mismatch. For another investigation, the BixSb2-xTe3 ingots with x=0.4, 0.45, 0.5 and 0.6. were fabricated by Bridgeman method at 750 ℃ for 12 hrs. We studied the effects of amount of Bi in BixSb2-xTe3 and the SPS process on the ZT enhancement. The experiment showed that for x >0.5, the thermal property changed from a curve to a relatively linear line at the end. The best ZT is 1.5 ingot at 300 K for x=0.45 specimen. The significant ZT improvement arises from the much-reduced electric resistivity. The lowest resistivity for x=0.45 specimen is mainly due to the highest carrier concentration than those with x=0.4, 0.5 and 0.6 ingots.