Analysis of Ce‐ and Yb‐Doped TAGS‐85 Materials with Enhanced Thermoelectric Figure of Merit

Doping of TAGS‐85 with 1 at% Ce or Yb forms a dilute magnetic semiconductor system with non‐interacting localized magnetic moments that obey the Curie law. X‐ray diffraction patterns and slight broadening in ¹²⁵Te NMR, attributed to paramagnetic effects, suggest that Ce and Yb atoms are incorporated into the lattice. ¹²⁵Te NMR spin‐lattice relaxation and Hall effect show similar hole concentrations of ≈10²¹ cm^?3. At 700 K, the electric conductivity of the Ce‐ and Yb‐doped samples is similar to that of neat TAGS‐85, while the thermal conductivity and the Seebeck coefficient are larger by 6% and 16%, respectively. Possible mechanisms responsible for the observed increase in thermopower may include i) formation of resonance states near the Fermi level and ii) carrier scattering by lattice distortions and/or by paramagnetic ions. Due to the increase in the Seebeck coefficient up to 205 μV K^?1, the thermoelectric power factor of Ce‐ and Yb‐doped samples reaches 36 μW cm^?1 K^?2, which is larger than that measured for neat TAGS‐85, 27 μW cm^?1 K^?2. The increase in the Seebeck coefficient overcomes the increase in the thermal conductivity, resulting in a total increase of the figure of merit by ≈25% at 700 K compared to that observed for neat TAGS‐85.     

Employing Interfaces with Metavalently Bonded Materials for Phonon Scattering and Control of the Thermal Conductivity in TAGS‐x Thermoelectric Materials

The thermoelectric compound (GeTe)_x(AgSbTe₂)_1?x, in short (TAGS‐x), is investigated with a focus on two stoichiometries, i.e., TAGS‐50 and TAGS‐85. TAGS‐85 is currently one of the most studied thermoelectric materials with great potential for thermoelectric applications. Yet, surprisingly, the lowest thermal conductivity is measured for TAGS‐50, instead of TAGS‐85. To explain this unexpected observation, atom probe tomography (APT) measurements are conducted on both samples, revealing clusters of various compositions and sizes. The most important role is attributed to Ag₂Te nanoprecipitates (NPs) found in TAGS‐50. In contrast to the Ag₂Te NPs, the matrix reveals an unconventional bond breaking mechanism. More specifically, a high probability of multiple events (PME) of ≈60% is observed for the matrix by APT. Surprisingly, the PME value decreases abruptly to ≈20–30% for the Ag₂Te NPs. These differences can be attributed to differences in chemical bonding. The precipitates' PME value is indicative of normal bonding, i.e., covalent bonding with normal optical modes, while materials with this unconventional bond breaking found in the matrix are characterized by metavalent bonding. This implies that the interface between the metavalently bonded matrix and covalently bonded Ag₂Te NP is partly responsible for the reduced thermal conductivity in TAGS‐50.     

High Thermoelectric Performance in Supersaturated Solid Solutions and Nanostructured n‐Type PbTe–GeTe

Sb‐doped and GeTe‐alloyed n‐type thermoelectric materials that show an excellent figure of merit ZT in the intermediate temperature range (400–800 K) are reported. The synergistic effect of favorable changes to the band structure resulting in high Seebeck coefficient and enhanced phonon scattering by point defects and nanoscale precipitates resulting in reduction of thermal conductivity are demonstrated. The samples can be tuned as single‐phase solid solution (SS) or two‐phase system with nanoscale precipitates (Nano) based on the annealing processes. The GeTe alloying results in band structure modification by widening the bandgap and increasing the density‐of‐states effective mass of PbTe, resulting in significantly enhanced Seebeck coefficients. The nanoscale precipitates can improve the power factor in the low temperature range and further reduce the lattice thermal conductivity (κ_lat). Specifically, the Seebeck coefficient of Pb_0.988Sb_0.012Te–13%GeTe–Nano approaches ?280 µV K^?1 at 673 K with a low κ_lat of 0.56 W m^?1 K^?1 at 573 K. Consequently, a peak ZT value of 1.38 is achieved at 623 K. Moreover, a high average ZT_avg value of ≈1.04 is obtained in the temperature range from 300 to 773 K for n‐type Pb_0.988Sb_0.012Te–13%GeTe–Nano.     

High‐Performance N‐type Mg3Sb2 towards Thermoelectric Application near Room Temperature

Se‐doped Mg_3.2Sb_1.5Bi_0.5‐based thermoelectric materials are revisited in this study. An increased ZT value ≈ 1.4 at about 723 K is obtained in Mg_3.2Sb_1.5Bi_0.49Se_0.01 with optimized carrier concentration ≈ 1.9 × 10¹⁹ cm^?3. Based on this composition, Co and Mn are incorporated for the manipulation of the carrier scattering mechanism, which are beneficial to the dramatically enhanced electrical conductivity and power factor around room temperature range. Combined with the lowered lattice thermal conductivity due to the introduction of effective phonon scattering centers in Se&Mn‐codoped sample, a highest room temperature ZT value ≈ 0.63 and a peak ZT value ≈ 1.70 at 623 K are achieved for Mg_3.15Mn_0.05Sb_1.5Bi_0.49Se_0.01, leading to a high average ZT ≈ 1.33 from 323 to 673 K. In particular, a remarkable average ZT ≈ 1.18 between the temperature of 323 and 523 K is achieved, suggesting the competitive substitution for the commercialized n‐type Bi₂Te₃‐based thermoelectric materials.     

Point Defect Engineering of High‐Performance Bismuth‐Telluride‐Based Thermoelectric Materials

Developing high‐performance thermoelectric materials is one of the crucial aspects for direct thermal‐to‐electric energy conversion. Herein, atomic scale point defect engineering is introduced as a new strategy to simultaneously optimize the electrical properties and lattice thermal conductivity of thermoelectric materials, and (Bi,Sb)₂(Te,Se)₃ thermoelectric solid solutions are selected as a paradigm to demonstrate the applicability of this new approach. Intrinsic point defects play an important role in enhancing the thermoelectric properties. Antisite defects and donor‐like effects are engineered in this system by tuning the formation energy of point defects and hot deformation. As a result, a record value of the figure of merit ZT of ≈1.2 at 445 K is obtained for n‐type polycrystalline Bi₂Te_2.3Se_0.7 alloys, and a high ZT value of ≈1.3 at 380 K is achieved for p‐type polycrystalline Bi_0.3Sb_1.7Te₃ alloys, both values being higher than those of commercial zone‐melted ingots. These results demonstrate the promise of point defect engineering as a new strategy to optimize thermoelectric properties.     

On Intensifying Carrier Impurity Scattering to Enhance Thermoelectric Performance in Cr‐Doped CeyCo4Sb12

The beneficial effect of impurity scattering on thermoelectric properties has long been disregarded even though possible improvements in power factor have been suggested by Ioffe more than a half century ago. Here it is theoretically and experimentally demonstrated that proper intensification of ionized impurity scattering to charge carriers can benefit the thermoelectric figure of merit (ZT) by increasing the Seebeck coefficient and decreasing the electronic thermal conductivity. The optimal strength of ionized impurity scattering for maximum ZT depends on the Fermi level and the density of states effective mass. Cr‐doping in Ce_yCo₄Sb₁₂ progressively increases the strength of ionized impurity scattering, and significantly improves the Seebeck coefficient, resulting in high power factors of 45 μW cm^?1 K^?2 with relatively low electrical conductivity. This effect, combined with the increased Ce‐filling fraction and thus decreased lattice thermal conductivity by charge compensation of Cr‐dopant, gives rise to a maximum ZT of 1.3 at 800 K and a large average ZT of 1.1 between 500 and 850 K, ≈30% and ≈20% enhancements as compared with those of Cr‐free sample, respectively. Furthermore, this study also reveals that carrier scattering parameter can be another fundamental degree of freedom to optimize electrical properties and improve thermal‐to‐electricity conversion efficiencies of thermoelectric materials.     

Engineering Thermal Conductivity for Balancing Between Reliability and Performance of Bulk Thermoelectric Generators

The nanostructuring approach has significantly contributed to the improving of thermoelectric figure‐of‐merit (ZT) by reducing lattice thermal conductivity. Even though it is an effective method to enhance ZT, the drastically lowered thermal conductivity in some cases can cause thermomechanical issues leading to decreased reliability of thermoelectric generators. Here, an engineering thermal conductivity (κ_eng) is defined as a minimum allowable thermal conductivity of a thermoelectric material in a module, and is evaluated to avoid thermomechanical failure and thermoelectric degradation of a device. Additionally, there is dilemma of determining thermoelectric leg length: a shorter leg is desired for higher W kg^?1, W cm^?3, and W The nanostructuring approach has significantly contributed to the improving of thermoelectric figure‐of‐merit (ZT) by reducing lattice thermal conductivity. Even though it is an effective method to enhance ZT, the drastically lowered thermal conductivity in some cases can cause thermomechanical issues leading to decreased reliability of thermoelectric generators. Here, an engineering thermal conductivity (κ_eng) is defined as a minimum allowable thermal conductivity of a thermoelectric material in a module, and is evaluated to avoid thermomechanical failure and thermoelectric degradation of a device. Additionally, there is dilemma of determining thermoelectric leg length: a shorter leg is desired for higher W kg^?1, W cm^?3, and W $^?1, but it raises the thermomechanical vulnerability issue. By considering a balance between the thermoelectric performance and thermomechanical reliability issues, it is discussed how to improve device reliability of thermoelectric generators and the engineering thermal conductivity of thermoelectric materials.     

Polaron Transport and Thermoelectric Behavior in La‐Doped SrTiO3 Thin Films with Elemental Vacancies

The electrodynamic properties of La‐doped SrTiO₃ thin films with controlled elemental vacancies are investigated using optical spectroscopy and thermopower measurement. In particular, a correlation between the polaron formation and thermoelectric properties of the transition metal oxide (TMO) thin films is observed. With decreasing oxygen partial pressure during the film growth (P(O₂)), a systematic lattice expansion is observed along with the increased elemental vacancy and carrier density, experimentally determined using optical spectroscopy. Moreover, an absorption in the mid‐infrared photon energy range is found, which is attributed to the polaron formation in the doped SrTiO₃ system. Thermopower of the La‐doped SrTiO₃ thin films can be largely modulated from –120 to –260 μV K^?1, reflecting an enhanced polaronic mass of ≈3 < m _polron/m < ≈4. The elemental vacancies generated in the TMO films grown at various P(O₂) influences the global polaronic transport, which governs the charge transport behavior, including the thermoelectric properties.     

Thermoelectric Properties of Co-Doped TiS<Subscript>2</Subscript>

The thermoelectric properties of cobalt-doped compounds Co _x Ti_1−x S₂ (0 ≤ x ≤ 0.3) prepared by solid-state reaction were investigated from 5 K to 310 K. It was found that the electric resistivity ρ and absolute thermopower |S| for all the doped compounds decreased significantly with increasing Co content over the whole temperature range investigated. The increased lattice thermal conductivity of the doped compounds would imply enhancement of the acoustic velocity. Moreover, the ZT value of the doped compounds was improved over the whole temperature range investigated, and specifically reached 0.03 at 310 K for Co_0.3Ti_0.7S₂, being about 66% larger than that of TiS₂.     

High Thermoelectric Performance in the Wide Band‐Gap AgGa1‐xTe2 Compounds: Directional Negative Thermal Expansion and Intrinsically Low Thermal Conductivity

A deficiency of Ga in wide band‐gap AgGa_1‐xTe₂ semiconductors (1.2 eV) can be used to optimize the electrical transport properties and reduce the thermal conductivity to achieve ZT > 1 at 873 K. First‐principles density functional theory calculations and a Boson peak observed in the low temperature heat capacity data indicate the presence of strong coupling between optical phonons with low frequency and heat carrying acoustical phonons, resulting in a depressed maximum of Debye frequency in the first Brillouin zone and low phonon velocities. Moreover, the Ag? Te bond lengths and Te? Ag? Te bond angles increase with rising temperature, leading to a significant distortion of the [AgTe₄]^7? tetrahedra, but an almost unmodified [GaTe₄]^5? tetrahedra. This behavior results in lattice expansion in the ab‐plane and contraction along the c‐axis, corresponding to the positive and negative Gruneisen parameters in the phonon spectral calculations. This effect gives rise to the large anharmonic behavior of the lattice. These factors together with the low frequency vibrations of Ag and Te atoms in the structure lead to an ultralow thermal conductivity of 0.18 W m^?1 K^?1 at 873 K.     

Charge‐Compensated Compound Defects in Ga‐containing Thermoelectric Skutterudites

Heavy doping changes an intrinsic semiconductor into a metallic conductor by the introduction of impurity states. However, Ga impurities in thermoelectric skutterudite CoSb₃ with lattice voids provides an example to the contrary. Because of dual‐site occupancy of the single Ga impurity charge‐compensated compound defects are formed. By combining first‐principle calculations and experiments, we show that Ga atoms occupy both the void and Sb sites in CoSb₃ and couple with each other. The donated electrons from the void‐filling Ga (Ga_VF) saturate the dangling bonds from the Sb‐substitutional Ga (Ga_Sb). The stabilization of Ga impurity as a compound defect extends the region of skutterudite phase stability toward Ga_0.15Co₄Sb_11.95 whereas the solid–solution region in other directions of the ternary phase diagram is much smaller. A proposed ternary phase diagram for Ga‐Co‐Sb is given. This compensated defect complex leads to a nearly intrinsic semiconductor with heavy Ga doping in CoSb₃ and a much reduced lattice thermal conductivity (κ_L) which can also be attributed to the effective scattering of both the low‐ and high‐frequency lattice phonons by the dual‐site occupant Ga impurities. Such a system maintains a low carrier concentration and therefore high thermopower, and the thermoelectric figure of merit quickly increases to 0.7 at a Ga doping content as low as 0.1 per Co₄Sb₁₂ and low carrier concentrations on the order of 10¹⁹ cm^?3.     

Understanding of the Extremely Low Thermal Conductivity in High‐Performance Polycrystalline SnSe through Potassium Doping

P‐type polycrystalline SnSe and K_0.01Sn_0.99Se are prepared by combining mechanical alloying (MA) and spark plasma sintering (SPS). The highest ZT of ≈0.65 is obtained at 773 K for undoped SnSe by optimizing the MA time. To enhance the electrical transport properties of SnSe, K is selected as an effective dopant. It is found that the maximal power factor can be enhanced significantly from ≈280 μW m^?1 K^?2 for undoped SnSe to ≈350 μW m^?1 K^?2 for K‐doped SnSe. It is also observed that the thermal conductivity of polycrystalline SnSe can be enhanced if the SnSe powders are slightly oxidized. Surprisingly, after K doping, the absence of Sn oxides at grain boundaries and the presence of coherent nanoprecipitates in the SnSe matrix contribute to an impressively low lattice thermal conductivity of ≈0.20 W m^?1 K^?1 at 773 K along the sample section perpendicular to pressing direction of SPS. This extremely low lattice thermal conductivity coupled with the enhanced power factor results in a record high ZT of ≈1.1 at 773 K along this direction in polycrystalline SnSe.     

High Thermoelectric Performance of Dually Doped ZnO Ceramics

A marked improvement in the thermoelectric performance of dense ZnO ceramics is achieved by employing a third element as a co-dopant with Al. Dual doping of ZnO with Al and Ga results in a drastic decrease in the thermal conductivity of the oxide, while the decrease in the electrical conductivity is relatively small. With the aid of a significant enhancement in the thermopower, the dually doped oxide shows thermoelectric figure of merit values, ZT, values of 0.47 at 1000 K and 0.65 at 1247 K at the composition Zn_0.96Al_0.02Ga_0.02O. These results appear to be the highest ZT values so far reported for bulk n-type oxides. Microscopic observation of the samples reveals a granular texture in the densely sintered oxide matrix, suggesting that considerable reduction of the thermal conductivity while maintaining high electrical conductivity could be achieved by such a bulk nanocomposite structure in the samples.     

Enhancement of Thermoelectric Figure‐of‐Merit by a Bulk Nanostructuring Approach

Recently a significant figure‐of‐merit (ZT) improvement in the most‐studied existing thermoelectric materials has been achieved by creating nanograins and nanostructures in the grains using the combination of high‐energy ball milling and a direct‐current‐induced hot‐press process. Thermoelectric transport measurements, coupled with microstructure studies and theoretical modeling, show that the ZT improvement is the result of low lattice thermal conductivity due to the increased phonon scattering by grain boundaries and structural defects. In this article, the synthesis process and the relationship between the microstructures and the thermoelectric properties of the nanostructured thermoelectric bulk materials with an enhanced ZT value are reviewed. It is expected that the nanostructured materials described here will be useful for a variety of applications such as waste heat recovery, solar energy conversion, and environmentally friendly refrigeration.     

Synthesis and Characterization of <Emphasis Type="Italic">p</Emphasis>-Type Pb<Subscript>0.5</Subscript>Sn<Subscript>0.5</Subscript>Te Thermoelectric Power Generation Elements by Mechanical Alloying

A mechanical alloying (MA) process to transform elemental powders into solid Pb_0.5Sn_0.5Te with thermoelectric functionality comparable to melt-alloyed material is described. The room-temperature doping level and mobility as well as temperature-dependent electrical conductivity, Seebeck coefficient, and thermal conductivity are reported. Estimated values of lattice thermal conductivity (0.7 W m⁻¹ K⁻¹) are lower than some reports of functional melt-alloyed PbSnTe-based material, providing evidence that MA can engender the combination of properties resulting in highly functional thermoelectric material. Though doping level and Sn composition have not been optimized, this material exhibits a ZT value >0.5 at 550 K.     

Thermoelectric Performance of Multiple-Doped Co4Sb12−x−y−z Ge x Te y S z Skutterudite Compounds

CoSb₃ skutterudites multiply doped with Ge, Te, and S were synthesized by solid-state reaction and spark plasma sintering. x-Ray diffraction studies revealed that Ge, Te, and S entered the lattice of the CoSb₃ compounds, and while Te increased the lattice volume, Ge and S decreased it. Compared with the undoped and single-doped CoSb₃ compounds, the thermal conductivity and lattice thermal conductivity are significantly suppressed due to greatly increased point defect scattering. It is found that S is more effective for decreasing the lattice thermal conductivity than Te and Ge. The highest thermoelectric figure of merit, ZT, exceeds 1.1 for the Co₄Sb_11.25Ge_0.05Te_0.63S_0.07 compound at 800 K.     

Mg3+δSbxBi2−x Family: A Promising Substitute for the State‐of‐the‐Art n‐Type Thermoelectric Materials near Room Temperature

The Bi₂Te_3?xSe_x family has constituted n‐type state‐of‐the‐art thermoelectric materials near room temperature (RT) for more than half a century, which dominates the active cooling and novel heat harvesting application near RT. However, the drawbacks of a brittle nature and Te‐content restricts the possibility for exploring potential applications. Here, it is shown that the Mg_3+δSb_xBi_2?x family ((ZT)_avg = 1.05) could be a promising substitute for the Bi₂Te_3?xSe_x family ((ZT)_avg = 0.9–1.0) in the temperature range of 50–250 °C based on the comparable thermoelectric performance through a synergistic effect from the tunable bandgap using the alloy effect and the suppressible Mg‐vacancy formation using an interstitial Mn dopant. The former is to shift the optimal thermoelectric performance to near RT, and the latter is helpful to partially decouple the electrical transport and thermal transport in order to get an optimal RT power factor. The positive temperature dependence of the bandgap suggests this family is also a superior medium‐temperature thermoelectric material for the significantly suppressed bipolar effect. Furthermore, a two times higher mechanical toughness, compared with the Bi₂Te_3?xSe_x family, allows for a promising substitute for state‐of‐the‐art n‐type thermoelectric materials near RT.     

Doping Effects on the Thermoelectric Properties of AgSbTe<Subscript>2</Subscript>

A doping study of ternary alloys AgSbTe₂ doped with excess AgTe, NaTe, NaSe, TlTe, BiTe, and excess Pb showed that carrier concentrations can be effectively manipulated. Measured thermopower and resistivity indicate a shift of the power factor peak toward the lower-temperature regime. The measured figure of merit ZT increases from 0.5 to 1.2 after doping with NaSe, and 1.05 with TlTe, at 400 K. We also show that doping with Bi and Pb has a negative effect on the thermoelectric properties of these alloys.     

Great Enhancement in the Thermopower of Ionic Liquid by a Metal-Organic Framework

To efficiently harvest the abundant waste heat on earth is of great significance for sustainable development. Thermoelectric materials can be used to directly convert heat into electricity, and ionic thermoelectric materials like ionic liquids (ILs) are considered as the next-generation thermoelectric materials. It is important to develop novel methods to improve the overall thermoelectric properties particularly the thermopower. Herein, the great enhancement in the thermopower of 1-ethyl-3-methylimidazolium dicyanamide (EMIM:DCA) is reported that is an IL by introducing zeolitic imidazolate framework (ZIF-8) that is a metal-organic framework (MOF) for the first time. The presence of 40 wt.% ZIF-8 can greatly increase the ionic thermopower of EMIM:DCA from 8.8 to 31.9 mV K⁻¹ at room temperature, and the ZIF-8/EMIM:DCA mixture at the ZIF-8 loading of 10 wt.% can exhibit a ZT_i value of 3.1, notably higher than that (0.59) of neat EMIM:DCA. The enhancement in the thermopower is attributed to the increase in the difference of the mobilities of EMIM⁺ and DCA⁻ by ZIF-8. Because DCA⁻ is smaller while EMIM⁺ is larger than the pore size of ZIF-8, the DCA⁻ transport is hindered by ZIF-8, while EMIM⁺ can bypass ZIF-8.     

Magnetic Field‐Enhanced Thermoelectric Performance in Dirac Semimetal Cd3As2 Crystals with Different Carrier Concentrations

The magneto‐thermoelectric figure of merit (ZT) in crystals of the topological Dirac semimetal Cd₃As₂ with different carrier concentrations is studied. The ZTs for all the crystals increase with the temperature and show maxima at high temperatures. Meanwhile, the temperatures corresponding to the ZT maxima increase with the carrier concentration. The limit to the improvement in ZT(T) at high temperature could be related to the unusual large enhancement in thermal conductivity at elevated temperatures. The bipolar effect and Dirac liquid behavior are presented as processes possibly responsible for the peculiar behavior of the thermal conductivity. Applying a transverse magnetic field initially leads to a dramatic enhancement and, subsequently, to a slight reduction in ZT for all the crystals. The maximum ZT achieved in a magnetic field increases with the carrier concentration and reaches 1.24 at 450 K in a magnetic field of 9 T for the crystal with the highest carrier concentration. It is expected that this work will be beneficial to the current interests in optimizing the thermoelectric properties of quantum topological materials.