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.     

The Role of Ionized Impurity Scattering on the Thermoelectric Performances of Rock Salt AgPbmSnSe2+m

This study reports on the successful synthesis and on the properties of polycrystalline AgPb_mSnSe_2+m (m = ∞, 100, 50, 25) samples with a rock salt structure. Between ≈160 and ≈400 K, the dominant scattering process of the carriers in this system changes from acoustic phonon scattering in PbSe to ionized impurity scattering in AgPb_mSnSe_2+m, which synergistically optimizes electrical and thermal transport properties. Thanks to the faint amount of AgSnSe₂, the Seebeck coefficient is enhanced by boosting the scattering factor, the electric conductivity is improved by the increase of the concentration of holes coupled to a limited degradation of their mobility, and the total thermal conductivity is reduced by suppressing bipolar thermal conductivity. Therefore, ZT of AgPb_mSnSe_2+m (m = 50) reaches 1.3 at 889 K. The mechanism suggested in this study opens new paths to improve the thermoelectric performances of other families of materials.     

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.     

Cu Intercalation and Br Doping to Thermoelectric SnSe2 Lead to Ultrahigh Electron Mobility and Temperature‐Independent Power Factor

Due to its single conduction band nature, it is highly challenging to enhance the power factor of SnSe₂ by band convergence. Here, it is reported that simultaneous Cu intercalation and Br doping induce strong Cu–Br interaction to connect SnSe₂ layers, otherwise isolated, via “electrical bridges.” Atom probe tomography analysis confirms a strong attraction between Cu intercalants and Br dopants in the SnSe₂ lattice. Density functional theory calculations reveal that this interaction delocalizes electrons confined around Sn? Se covalent bonds and enhances charge transfer across the SnSe₂ slabs. These effects dramatically increase electron mobility and concentration. Polycrystalline SnCu_0.005Se_1.98Br_0.02 shows even higher electron mobility than pristine SnSe₂ single crystal and the theoretical expectation. This results in significantly improved electrical conductivity without reducing effective mass and Seebeck coefficient, thereby leading to the highest power factor of ≈12 µW cm^?1 K^?2 to date for polycrystalline SnSe₂ and SnSe. It even surpasses the value for the state‐of‐the‐art n‐type SnSe_0.985Br_0.015 single crystal at elevated temperatures. Surprisingly, the achieved power factor is nearly independent of temperature ranging from 300 to 773 K. The engineering thermoelectric figure of merit ZT_eng for SnCu_0.005Se_1.98Br_0.02 is ≈0.25 between 773 and 300 K, the highest ZT_eng ever reported for any form of SnSe₂‐based thermoelectric materials.     

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.     

BiSbTe‐Based Nanocomposites with High ZT: The Effect of SiC Nanodispersion on Thermoelectric Properties

Thermoelectric materials have potential applications in energy harvesting and electronic cooling devices, and bismuth antimony telluride (BiSbTe) alloys are the state‐of‐the‐art thermoelectric materials that have been widely used for several decades. It is demonstrated that mixing SiC nanoparticles into the BiSbTe matrix effectively enhances its thermoelectric properties; a high dimensionless figure of merit (ZT) value of up to 1.33 at 373 K is obtained in Bi_0.3Sb_1.7Te₃ incorporated with only 0.4 vol% SiC nanoparticles. SiC nanoinclusions possessing coherent interfaces with the Bi_0.3Sb_1.7Te₃ matrix can increase the Seebeck coefficient while increasing the electrical conductivity, in addition to its effect of reducing lattice thermal conductivity by enhancing phonon scattering. Nano‐SiC dispersion further endows the BiSbTe alloys with better mechanical properties, which are favorable for practical applications and device fabrication.     

High-Performance (Ag<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>SbTe<Subscript><Emphasis Type="Italic">x</Emphasis>/2+1.5</Subscript>)<Subscript>15</Subscript>(GeTe)<Subscript>85</Subscript> Thermoelectric Materials Prepared by Melt Spinning

A new preparation process combining melt spinning and hot pressing has been developed for the (Ag _x SbTe _x/2+1.5)₁₅(GeTe)₈₅ (TAGS-85) system. Compared with samples prepared by the traditional air-quenching and hot-pressing method, electrical conductivity and thermal conductivity are lowered. The thermoelectric performance of the TAGS-85 samples varied with changing Ag content and reached the highest ZT of 1.48 when x was 0.8 for the melt-spun sample, compared with the maximum ZT of 1.36 for the air-quenched sample. The Seebeck coefficient of the melt-spun TAGS-85 alloys was improved, while both the electrical conductivity and thermal conductivity were decreased. The net result of this process is to effectively enlarge the temperature span of ZT > 1, which will benefit industrial application.     

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.     

Vacancy Manipulation Induced Optimal Carrier Concentration,Band Convergence and Low Lattice Thermal Conductivity in Nano-Crystalline SnTe Yielding Superior Thermoelectric Performance

Synergetic optimization of electrical and thermal transport properties is achieved for SnTe-based nano-crystalline materials. Gd doping is able to suppress the Sn vacancy, which is confirmed by positron annihilation measurements and corresponding theoretical calculations. Hence, the optimal hole carrier concentration is obtained, leading to the improvement of electrical transport performance and simultaneous decrease of electronic thermal conductivity. In addition, the incremental density of states effective mass m* in SnTe is realized by the promotion of the band convergence via Gd doping, which is further confirmed by the band structure calculation. Hence, the enhancement of the Seebeck coefficient is also achieved, leading to a high power factor of 2922 µW m⁻¹ K⁻² for Sn_0.96Gd_0.04Te at 900 K. Meanwhile, substantial suppression of the lattice thermal conductivity is observed in Gd-doped SnTe, which is originated from enhanced phonon scattering by multiple processes including mass and strain fluctuations due to the Gd doping, scattering of grain boundaries, nano-pores, and secondary phases induced by Gd doping. With the decreased phonon mean free path and reduced average phonon group velocity, a rather low lattice thermal conductivity is achieved. As a result, the synergetic optimization of the electric and thermal transport properties contributes to a rather high ZT value of ≈1.5 at 900 K, leading to the superior thermoelectric performance of SnTe-based nanoscale polycrystalline materials.     

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.     

Controlling Electrostatic Interaction in PEDOT:PSS to Overcome Thermoelectric Tradeoff Relation

A high power factor must be achieved to improve the thermoelectric (TE) output of organic TE materials though the tradeoff between electrical conductivity and the Seebeck coefficient is a serious obstacle to the further development of these materials. Here, systematic control of the electrostatic interaction between a conducting polymer and a dopant induces a positive deviation from this TE tradeoff relation so that the electrical conductivity and the Seebeck coefficient simultaneously increase. Upon reduction of the electrostatic interaction, substantial changes in the film morphology, chain conformation, and crystalline ordering are observed, all of which critically affect the TE charge transport. As a result, the electrostatic interaction control is found to be an effective strategy to enhance the power factor, overcoming the tradeoff between TE parameters. Adapting this strategy to poly(3,4‐ethylenedioxythiophene):polystyrene‐sulfonate results in a remarkable power factor (=700.2 µW m^?1 K^?2 ) and figure of merit ZT (=0.25).     

Increase in the Thermoelectric Efficiency of the Disordered Phase of Layered Antiferromagnetic CuCrS<Subscript>2</Subscript>

The thermoelectric figure of merit (ZT) of the layered antiferromagnetic compound CuCrS₂ is further improved with increase in the Cr-vacancy disorder on sintering above 900°C. X-ray photoelectron spectroscopy and x-ray diffraction refinement results for different samples show that the chromium atoms are transferred from the filled layers to the vacant sites between the layers. This atomic disorder increases the electrical conductivity (σ) due to self-doping of the charge carriers and reduces thermal conductivity (κ) due to increase in phonon scattering. The Seebeck coefficient (S) is p-type and remains nearly temperature independent with values between 150 μV/K and 450 μV/K due to electronic doping in different samples.     

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.     

Effects of YSZ Additions on Thermoelectric Properties of Nb-Doped Strontium Titanate

The effect of yttria-stabilized zirconia (YSZ) with a low thermal conductivity on the thermoelectric properties of Nb-doped SrTiO₃ bulk materials, which were fabricated by the conventional normal pressure sintering method in an Ar atmosphere, was examined. YSZ additions reduced the thermal conductivity but significantly enhanced the electrical conductivity. However, the Seebeck coefficient was nearly independent of YSZ content. Thus, the ZT value was enhanced, and a sample with 3 wt.% YSZ displayed the maximum ZT value, 0.21, at 900 K. Additionally, the reason for the reduced thermal conductivity and enhanced electrical conductivity by YSZ additions was investigated in detail.     

Theoretical and experimental investigations of the thermoelectric properties of Al-, Bi- and Sn-doped ZnO

In this paper, the thermoelectric properties of ZnO doped with Al, Bi and Sn were investigated by combining experimental and theoretical methods. The average Seebeck coefficient of Bi doped ZnO over the measured temperature range is improved from −90 to −497 μV/K. However, segregation of Bi₂O₃ in ZnO:Bi sample, confirmed by FESEM, lead to enormous grain growth and low electrical conductivity, which makes Bi is not a good dopant to improve ZT value of ZnO. As a 4+ valence cation, Sn doping actually show an increase in carrier concentration to 10²⁰ cm⁻³, further enhancing the electrical conductivity. Unfortunately, the Seebeck coefficient of ZnO:Sn samples is even lower than pure ZnO sample, which lead to a low ZT value. As for ZnO:Al sample, with nearly no change in lattice thermal conductivity, electrical conductivity and Seebeck coefficient were both enhanced. Threefold enhancement in ZT value has been achieved in ZnO:Al sample at 760 °C compared with pure ZnO.     

Nanoscale FeS2 (Pyrite) as a Sustainable Thermoelectric Material

We have synthesized undoped, Co-doped (up to 5%), and Se-doped (up to 4%) FeS₂ materials by mechanical alloying in a planetary ball mill and investigated their thermoelectric properties from room temperature (RT) to 600 K. With decreasing particle size, the undoped FeS₂ samples showed higher electrical conductivity, from 0.02 S cm^?1 for particles with 70 nm grain size up to 3.1 S cm^?1 for the sample with grain size of 16 nm. The Seebeck coefficient of the undoped samples showed a decrease with further grinding, from 128 μV K^?1 at RT for the sample with 70-nm grains down to 101 μV K^?1 for the sample with grain size of 16 nm. The thermal conductivity of the 16-nm undoped sample lay within the range from 1.3 W m^?1 K^?1 at RT to a minimal value of 1.2 W m^?1 K^?1 at 600 K. All doped samples showed improved thermoelectric behavior at 600 K compared with the undoped sample with 16 nm particle size. Cobalt doping modified the p-type semiconducting behavior to n-type and increased the thermal conductivity (2.1 W m^?1 K^?1) but improved the electrical conductivity (41 S cm^?1) and Seebeck coefficient (-129 μV K^?1). Isovalent selenium doping led to a slightly higher thermal conductivity (1.7 W m^?1 K^?1) as well as to an improved electrical conductivity (26 S cm^?1) and Seebeck coefficient (110 μV K^?1). The ZT value of FeS₂ was increased by a factor of five by Co doping and by a factor of three by Se doping.     

The Impact of Nanostructuring on the Thermal Conductivity of Thermoelectric CoSb3

The high concentration of grain boundaries provided by nanostructuring is expected to lower the thermal conductivity of thermoelectric materials, which favors an increase in their thermoelectric figure‐of‐merit, ZT. A novel chemical alloying method has been used for the synthesis of nanoengineered‐skutterudite CoSb₃. The CoSb₃ powders were annealed for different durations to obtain a set of samples with different particle sizes. The samples were then compacted into pellets by uniaxial pressing under various conditions and used for the thermoelectric characterization. The transport properties were investigated by measuring the Seebeck coefficient and the electrical and thermal conductivities in the temperature range 300 K to 650 K. A substantial reduction in the thermal conductivity of CoSb₃ was observed with decreasing grain size in the nanometer region. For an average grain size of 140 nm, the thermal conductivity was reduced by almost an order of magnitude compared to that of a single crystalline or highly annealed polycrystalline material. The highest ZT value obtained was 0.17 at 611 K for a sample with an average grain size of 220 nm. The observed decrease in the thermal conductivity with decreasing grain size is quantified using a model that combines the macroscopic effective medium approaches with the concept of the Kapitza resistance. The compacted samples exhibit Kapitza resistances typical of semiconductors and comparable to those of Si–Ge alloys.     

Design of High‐Performance Disordered Half‐Heusler Thermoelectric Materials Using 18‐Electron Rule

Ternary half‐Heusler (HH) alloys display intriguing functionalities ranging from thermoelectric to magnetic and topological properties. For thermoelectric applications, stable HH alloys with a nominal valence electron count (VEC) of 18 per formula or defective HH alloys with a VEC of 17 or 19 are assumed to be promising candidates. Inspired by the pioneering efforts to design a TiFe_0.5Ni_0.5Sb double HH alloy by combining 17‐electron TiFeSb and 19‐electron TiNiSb HH alloys, both high‐performance n‐type and p‐type materials based on the same parent TiFe_0.5Ni_0.5Sb are developed. First‐principles calculation results demonstrate their beneficial band structure having a high band degeneracy that contributes to their large effective mass and thereby maintains their high Seebeck coefficient values. Due to the strong Fe/Ni disorder effect, TiFe_0.5Ni_0.5Sb exhibits a much lower lattice thermal conductivity than does TiCoSb, consistent with very recently reported results. Furthermore, tuning the ratio of Fe and Ni leads to achieving both p‐ and n‐types, and alloying Ti by Hf further enhances the thermoelectric performance significantly. A peak ZT of ≈1 and ≈0.7 at 973 K are achieved in the p‐type and n‐type based on the same parent, respectively, which are beneficial and promising for real applications.     

Thermoelectric Power and <Emphasis Type="Italic">ZT</Emphasis> in Conducting Organic Semiconductor

A recent report on poly(3,4-ethylenedioxythiophene-tosylate) (PEDOT.Tos) suggested that the thermoelectric figure of merit (ZT) could be enhanced when the percentage oxidation was chemically altered. This invokes the question of whether the carrier density or the mobility was modified. In this work, we analyzed data reported by Bibnova et al. (Nat. Mater. 10, 429, 2011) and extracted the transport parameters using three-dimensional (3D) and two-dimensional (2D) models. Our results indicate that the increase in the power factor (S ² σ) was due primarily to upward extension in the range of thermoelectric power. A changeover from lattice scattering to ionized impurity scattering in PEDOT.Tos allowed the equation governing the thermoelectric power to be valid at higher carrier densities, resulting in an increase in the power factor. ZT was also enhanced in PEDOT.Tos due to the low intrinsic thermal conductivity (~0.37 W/m K). The peak value of ZT (~0.3) was found close to the regime where the semiconductor turned “metallic,” beyond which ZT would decrease. We are of the opinion that charge-to-charge scattering (which normally would lower the power factor in highly doped semiconductors) remain subdued in PEDOT.Tos due potentially to electronic screening and a lack of long-range order. We used the reported data to compute the carrier density and mobility assuming ionized impurity scattering and found the peak power factor to occur for carrier density of ~1 × 10²⁶ m⁻³ and mobility of ~5 × 10⁻⁴ m²/V s.