High Temperature Thermoelectric Research Articles

Comprehensive investigation of Li-based novel quaternary Heusler LiTiPdZ (Z = Al, Ga, In) compounds for thermoelectric performance

In the present article, we used Density Functional Theory and the Boltzmann transport equation to study the structural, electronic, and thermoelectric (TE) properties along with phonon dynamics of recently discovered LiTiPdZ (Z = Al, Ga, In) quaternary Heusler (QH) compounds. We applied generalized gradient approximations (GGA) for band structure and density of states (DOS) calculations. Comprehensive investigations of electronic structure reveal that an indirect band gap of 0.77 eV, 0.793 eV and 0.611 eV for LiTiPdAl, LiTiPdGa, and LiTiPdIn, is there reflecting the semiconducting nature of these compounds. We find that Pd-4d states contribute to the conduction band DOS while Ti-3d states contribute significantly to DOS near Fermi energy (EF) in both valence and conduction band. Phonon dispersion spectra show that all the studied compounds are dynamically stable, as obtained frequency is only in positive range. We have calculated thermoelectric properties up to a fairly high temperature (1600 K), to check the compatibility of these compounds for high temperature TE application. A high value of ZT (∼0.60 1600K) proposes these compounds as potential candidates for high temperature TE applications.

Thermoelectric properties of heavily Co-doped β-FeSi2

Element doping is a widely employed strategy to enhance the thermoelectric (TE) properties of various materials. β-FeSi2 is a promising low-cost high-temperature TE material with exceptional thermal stability; however, the doping limit of β-FeSi2 is usually very low, which limits the tunability of electrical and thermal properties. Recently, a high doping content of 0.16 in β-FeSi2 has been achieved by the introduction of iridium (Ir), leading to the highest reported figure of merit (zT) of 0.6 in β-FeSi2. Motivated by the successful heavy doping with Ir, this work aims to explore element heavy doping in β-FeSi2 with cobalt (Co), a cheaper, more readily available dopant with a smaller atomic radius and closer electronegativity to iron (Fe). In this study, we successfully obtained a record-high doping content of 0.24 in Co-doped β-FeSi2 through a prolonged annealing process. Despite the absence of a substantial enhancement in the zT of Co-doped β-FeSi2 at high doping levels, with a maximum zT of 0.3 at 900 K in Fe0.92Co0.08Si2, we observed a transition in the carrier transport mechanism as a function of Co doping content, attributed to changes in the band structure. At a low Co doping content (x ≤ 0.12), Fe1–xCoxSi2 demonstrates dominant carrier transport via impurity levels within the band gap, exhibiting hopping conduction. As the Co doping content increases (x > 0.16), the impurity levels overlap and form an impurity band, and the carrier transport turns into the impurity band conduction. The observed band conduction behavior of Fe1–xCoxSi2 (x > 0.16) mirrors that of Ir-doped β-FeSi2, but Fe1–xCoxSi2 shows much lower mobility, which can be attributed to the localized feature of the impurity band introduced by the Co doping. Overall, this study provides insights into the heavy Co doping and its influence on the TE properties and carrier conduction mechanisms in β-FeSi2, helpful for the further development of this TE system.

Lone-pair electron-induced low lattice thermal conductivity and excellent thermoelectric performance of AuX (X = S, Se, Te) monolayers

We present a detailed study on the phonon thermal transport and thermoelectric (TE) properties of gold monochalcogenide AuX (X = S, Se, Te) monolayers via first-principles calculations and the Boltzmann transport theory. At room temperature, the calculated lattice thermal conductivity (κl) values in the x-direction (y-direction) were determined to be 12.66 (3.59), 6.06 (1.23), and 3.02 (0.40) W/(m·K) for the AuS, AuSe, and AuTe monolayers, respectively. The analysis of scattering matrix elements and anharmonic scattering rates suggested that the presence of strong bond anharmonicity leads to low κl values. This anharmonicity was induced by the nonlinear electrostatic repulsive force between lone-pair electrons (LPEs) surrounding the chalcogen atom and adjacent bonding electron. Furthermore, the AuS monolayer exhibited the highest bond anharmonicity among the three monolayers. This can be attributed to the reduced strength of the electrostatic repulsive force when electronegativity decreased from S to Se and Te. Although the AuS monolayer exhibited the strongest bond anharmonicity, its κl was still the largest, demonstrating that among the factors that influence κl, harmonic factors have a greater effect than anharmonic parameters. When the atomic mass was increased, the phonon frequencies, phonon group velocities, and κl decreased. Benefiting from low κl induced by LPEs, the maximum ZT values of p-type doped AuSe and AuTe monolayers exceeded 1.0 and 2.0 at T = 800 K, respectively. These results not only confirmed that the introduction of LPEs can reduce the lattice thermal conductivity and enhance the TE performance of 2D materials, but also demonstrated the promising potential of the 2D AuX family for applications in high-temperature TE devices.

Oxygen vacancy-activated thermoelectric properties of ZnO ceramics

Understanding the structural and thermoelectric (TE) properties of a pure material is essential for developing a practical approach to improve its TE performance. This study focuses on the high-temperature TE properties of ZnO ceramics synthesized by the spark plasma sintering (SPS) technique. The analyses of crystallinity and microstructure along with photoluminescence and Raman spectroscopy indicated an increase in oxygen vacancy in the ZnO ceramics with SPS temperature, which resulted in unit-cell shrinkage, lattice modification, grain densification, and TE modification. Specifically, oxygen vacancies were found to be a crucial factor affecting the TE performance of the spark-plasma-sintered ZnO ceramics at temperatures exceeding 773 K. Oxygen vacancies can act as carrier donors when they are ionized, contributing to an increase in electrical conductivity and a decrease in thermal conductivity. Additionally, this study proposes a potential way to engineer native defects in ZnO ceramics by controlling the SPS process.

(Invited) Macroscopically Aligned Carbon Nanotubes for Photonics, Electronics, and Thermoelectrics

The remarkable flexibility, stable chemical structure, and extraordinary thermal, electrical, and optical properties of carbon nanotubes (CNTs) are promising for a variety of applications in flexible and/or high-temperature electronics, optoelectronics, and thermoelectrics, including wearables, refractory photonics, and waste heat harvesting. However, the long-standing goal in the preparation of CNT ensembles is how to maintain the extraordinary properties of individual CNTs on a macroscopic scale. The polydispersity and randomness remain two main challenges. Here, we will discuss different methods for creating macroscopically aligned CNTs, including spontaneous formation of wafer-scale aligned CNT films via controlled vacuum filtration and production of ultrahigh-conductivity CNT fibers and films through solution spinning and coating. We will then describe the optical, dc and ac electrical, thermal, and thermoelectric properties of these materials. These results are promising for device applications in various fields such as flexible CNT broadband detectors, spectrally selective thermal emitters, and thermoelectric devices.

Thermoelectric properties of pseudobrookite-based ceramics prepared from natural Fe-Ti-rich heavy mineral sand concentrate

Pseudobrookites (Fe2TiO5-FeTi2O5) are promising candidates for high-temperature oxide thermoelectrics. In this work, we used natural Fe-Ti-rich heavy mineral sand (HMS) as an abundant and environmentally friendly raw material for the preparation of pseudobrookite-based ceramics. The main components of the initial powder were ilmenite (FeTiO3) and pseudorutile (Fe2Ti3O9) with various degrees of alteration. Pre-oxidation of the as-received powder was used for modification of the Fe2+:Fe3+ ratio and exsolution of rutile. The starting powders were densified by conventional sintering (CS; 1200 °C, 5 h, pressureless) and spark plasma sintering (SPS; 1100 °C, 5 min, 150 MPs) in argon. The thermoelectric properties of the sintered compacts depend mainly on the Fe:Ti ratio, the Fe2+:Fe3+ ratio, and the fraction and distribution of rutile in the microstructures. The samples exhibit comparable properties as the pseudobrookite-based ceramics prepared from high-purity chemicals indicating that, with some further optimization, natural Fe-Ti-rich HMS are an interesting alternative for the preparation of pseudobrookite-based ceramics for thermoelectric applications.

Improved High Temperature Thermoelectric Properties in Misfit Ca3Co4O9 by Thermal Annealing

Ca3Co4O9, a p-type thermoelectric material based on transition-metal oxides, has garnered significant interest due to its potential in thermoelectric applications. Its unique misfit-layered crystal structure contributes to low thermal conductivity and a high Seebeck coefficient, leading to a thermoelectric figure of merit (zT) of ≥1 at 1000 K. Conventionally, it has been believed that thermopower reaches its upper limit above 200 K. However, our thermopower measurements on polycrystalline Ca3Co4O9 samples have revealed an unexpected increase in thermopower above 380 K. In this study, we investigate the effects of high oxygen pressure annealing on Ca3Co4O9 and provide an explanation based on the mixed oxide states of cobalt and carrier hopping. Our results demonstrate that annealing induces modifications in the defect chemistry of Ca3Co4O9, leading to a decrease in electron hopping probability and the emergence of a thermal activation-like behavior in thermopower. These findings carry significant implications for the design and optimization of thermoelectric materials based on misfit cobaltates, opening new avenues for enhanced thermoelectric performance.

Thermoelectric performance of Zintl compound KMgBi with layered structure

Zintl compounds are potential candidates for thermoelectric (TE) materials because of their excellent electronic transport combined with low thermal conductivity. We have systematically investigated the thermal, electronic transport, and TE properties of the anisotropic orthorhombic KMgBi crystal on the basis of first-principles calculations together with self-consistent phonon theory, the compressed sensing technique, and the Boltzmann transport equation. When predicting electron transport parameters, we take into account the impacts of acoustic deformation potential scattering, polar optical phonon scattering, and ionized impurity scattering on electron relaxation times. Strikingly, the layered structure of the Zintl compound KMgBi results in the material exhibiting strong anisotropy. This layered structure provides a good transport channel for electrons along the a (b)-axis, which results in a large difference in electrical conductivity and thermal conductivities between the a (b)-axis and the c-axis. Because of the high power factor obtained along the a (b)-axis, the figure of merit (ZT) is expected to reach 1.5 at 600 K and KMgBi is a promising candidate for high-temperature TE applications.

Microstructure and High-Temperature Thermoelectric Performance of InxCo4Sb12 Fabricated via Microwave Synthesis Combined with Spark Plasma Sintering

Microstructure and High-Temperature Thermoelectric Performance of InxCo4Sb12 Fabricated via Microwave Synthesis Combined with Spark Plasma Sintering

Theoretical determination of superior high-temperature thermoelectricity in an n-type doped 2H-ZrI2 monolayer.

Two-dimensional materials with a competitive figure of merit zT are extremely desirable for the fabrication of thermoelectric modules. In the present work, we systematically evaluated the thermoelectricity of monolayer 2H-ZrI2 through first-principles calculations and semiclassical Boltzmann transport theory. Apart from its all-round structural stability and feasibility of experimental preparation, the semiconducting material with a moderate indirect bandgap of 1.07 eV at the HSE06 level exhibits an acceptable lattice thermal conductivity κL of 6.69 W m-1 K-1 at 900 K contributed dominantly by acoustic modes. The four-phonon scattering is found to exert a minor effect on the κL of the monolayer. Moreover, a quite large power factor of up to 147.89 mW m-1 K-2 can be achieved due to the conduction band valley degeneracy near the Fermi level. These transport coefficients eventually give rise to a significant optimal n-type zT value as high as 3.57 at 900 K at a certain experimentally achievable electron doping concentration. Our study demonstrates the potential application of monolayer 2H-ZrI2 in high-temperature thermoelectric devices.

Coupling modification of Fermi level, band flattening and lattice defects to approach outstanding thermoelectric performance of ZnO films via tuning In and Ga incorporation

Band structure modification is found one of the state-of-the-art strategies to control electrical, thermal transport properties, and optimize performance of thermoelectric (TE) materials. Despite being a high-temperature n-type TE material, low-dimensional ZnO structures, specifically thin films normally possess a poor performance due to instability, low electrical, and high thermal conductivities. Herein, it is found that the trade-offs between TE parameters of ZnO films can be simultaneously abated by co-doping In and Ga. The dual incorporation of In and Ga enhances crystallinity, thermal stability, and TE properties up to 573 K. Tuning In and Ga contents not only optimizes carrier concentration associating with Fermi level modification, but also engineers lattice defects contributing to scattering transport mechanisms. Furthermore, the In3+ compensation at substitutional sites, specifically at high temperature, significantly increases density-of-state effective mass due to conduction band flattening. As a result, the coupling modification of Fermi level, band flattening, and lattice defects leads to maintaining electrical conductivity at a medium degree, increasing Seebeck coefficient, and decreasing thermal conductivity, respectively. The TE dimensionless figure of merit (ZT) and power factor (PF) of the films deposited from the In0.01Ga0.04Zn99.95O compound significantly boost to 0.2 and 745.2 µW/mK2 at 573 K, respectively. These values are 1328 and 536% higher than pristine ZnO film; 400 and 258% greater than Ga single-doped ZnO film, respectively. It proposes that our ZnO-based thin films approach the high ZT region (ZT ≥ 0.2) of advanced nanostructured ZnO-based bulks.

(Invited, Digital Presentation) Macroscopically Aligned Carbon Nanotubes for Photonics, Electronics, and Thermoelectrics

The remarkable flexibility, stable chemical structure, and extraordinary thermal, electrical, and optical properties of carbon nanotubes (CNTs) are promising for a variety of applications in flexible and/or high-temperature electronics, optoelectronics, and thermoelectrics, including wearables, refractory photonics, and waste heat harvesting [1]. However, the long-standing goal in the preparation of CNT ensembles is how to maintain the extraordinary properties of individual CNTs on a macroscopic scale. The polydispersity and randomness remain two main challenges.Here, we will discuss different methods for creating macroscopically aligned CNTs, including spontaneous formation of wafer-scale aligned CNT films via controlled vacuum filtration [2-4] and production of ultrahigh-conductivity CNT fibers and films through solution spinning and coating [5,6]. We will then describe the optical [2,7-11], dc and ac electrical [2,12-17], thermal [18], and thermoelectric [19-21] properties of these materials. These results are promising for device applications in various fields such as flexible CNT broadband detectors [22-26], spectrally selective thermal emitters [11], and thermoelectric devices [20,21]. W. Gao et al., “Macroscopically Aligned Carbon Nanotubes for Flexible and High-Temperature Electronics, Optoelectronics, and Thermoelectrics,” Journal of Physics D: Applied Physics 53, 063001 (2020).X. He et al., “Wafer-Scale Monodomain Films of Spontaneously Aligned Single-Walled Carbon Nanotubes,” Nature Nanotechnology 11, 633 (2016).W. Gao and J. Kono, “Science and Applications of Wafer-Scale Crystalline Carbon Nanotube Films Prepared through Controlled Vacuum Filtration,” Royal Society Open Science 6, 181605 (2019).N. 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Katsutani et al., “Direct Observation of Cross-Polarized Excitons in Aligned Single-Chirality Single-Wall Carbon Nanotubes,” Physical Review B 99, 035426 (2019).W. Gao et al., “Macroscopically Aligned Carbon Nanotubes as a Refractory Platform for Hyperbolic Thermal Emitters,” ACS Photonics 6, 1602 (2019).X. Wang et al., “High-Ampacity Power Cables of Tightly-Packed and Aligned Carbon Nanotubes,” Advanced Functional Materials 24, 3241 (2014).A. Zubair et al., “Carbon Nanotube Fiber Terahertz Polarizer,” Applied Physics Letters 108, 141107 (2016).D. Tristant et al., “Enlightening the Ultrahigh Electrical Conductivities of Doped Double-Wall Carbon Nanotube Fibers by Raman Spectroscopy and First-Principles Calculations,” Nanoscale 18, 19668 (2016).N. Komatsu et al., “Modulation-Doped Multiple Quantum Wells of Aligned Single-Wall Carbon Nanotubes,” Advanced Functional Materials 27, 1606022 (2017).F. R. G. Bagsican et al., “Terahertz Excitonics in Carbon Nanotubes: Exciton Autoionization and Multiplication,” Nano Letters 20, 3098 (2020).A. Baydin et al., “Giant Terahertz Polarization Rotation in Ultrathin Films of Aligned Carbon Nanotubes,” Optica 8, 760 (2021).S. Yamaguchi et al., “One-Directional Thermal Transport in Densely Aligned Single-Wall Carbon Nanotube Films,” Applied Physics Letters 115, 223104 (2019).K. Fukuhara et al., “Isotropic Seebeck Coefficient of Aligned Single-Wall Carbon Nanotube Films,” Applied Physics Letters 113, 243105 (2018).Y. Ichinose et al., “Solving the Thermoelectric Trade-Off Problem with Metallic Carbon Nanotubes,” Nano Letters 19, 7370 (2019).N. Komatsu et al., “Macroscopic Weavable Fibers of Carbon Nanotubes with Giant Thermoelectric Power Factor,” Nature Communications 12, 4931 (2021).S. Nanot et al., “Broadband, Polarization-Sensitive Photodetector Based on Optically-Thick Films of Macroscopically Long, Dense, and Aligned Carbon Nanotubes,” Scientific Reports 3, 1335 (2013).X. He et al., “Photothermoelectric p-n Junction Photodetector with Intrinsic Broadband Polarimetry Based on Macroscopic Carbon Nanotube Films,” ACS Nano 7, 7271 (2013).X. He et al., “Carbon Nanotube Terahertz Detector,” Nano Letters 14, 3953 (2014).X. He, F. Léonard, and J. Kono, “Uncooled Carbon Nanotube Photodetectors,” Advanced Optical Materials 3, 989 (2015).A. Zubair et al., “Carbon Nanotube Woven Textile Photodetector,” Physical Review Materials 2, 015201 (2018).

Potential of Recycled Silicon and Silicon-Based Thermoelectrics for Power Generation

Thermoelectrics can convert waste heat to electricity and vice versa. The energy conversion efficiency depends on materials figure of merit, zT, and Carnot efficiency. Due to the higher Carnot efficiency at a higher temperature gradient, high-temperature thermoelectrics are attractive for waste heat recycling. Among high-temperature thermoelectrics, silicon-based compounds are attractive due to the confluence of light weight, high abundance, and low cost. Adding to their attractiveness is the generally defect-tolerant nature of thermoelectrics. This makes them a suitable target application for recycled silicon waste from electronic (e-waste) and solar cell waste. In this review, we summarize the usage of high-temperature thermoelectric generators (TEGs) in applications such as commercial aviation and space voyages. Special emphasis is placed on silicon-based compounds, which include some recent works on recycled silicon and their thermoelectric properties. Besides materials design, device designing considerations to further maximize the energy conversion efficiencies are also discussed. The insights derived from this review can be used to guide sustainable recycling of e-waste into thermoelectrics for power harvesting.

Improved High-Temperature Thermoelectric Properties of Dual-Doped Ca3Co4O9.

Layered structured Ca3Co4O9 has displayed great potential for thermoelectric (TE) renewable energy applications, as it is nontoxic and contains abundantly available constituent elements. In this work, we study the crystal structure and high-temperature TE properties of Ca3–2yNa2yCo4–yMoyO9 (0 ≤ y ≤ 0.10) polycrystalline materials. Powder X-ray diffraction (XRD) analysis shows that all samples are single-phase samples and without any noticeable amount of the secondary phase. X-ray photoelectron spectroscopic (XPS) measurements depict the presence of a mixture of Co3+ and Co4+ valence states in these materials. The Seebeck coefficient (S) of dual-doped materials is significantly enhanced, and electrical resistivities (ρ) and thermal conductivities (κ) are decreased compared to the pristine compound. The maximum thermoelectric power factor (PF = S2/ρ) and dimensionless figure of merit (zT) obtained for the y = 0.025 sample at 1000 K temperature are ∼3.2 × 10–4 W m–1 K–2 and 0.27, respectively. The zT value for Ca2.95Na0.05Co3.975Mo0.025O9 is about 2.5 times higher than that of the parent Ca3Co4O9 compound. These results demonstrate that dual doping of Na and Mo cations is a promising strategy for improving the high-temperature thermoelectric properties of Ca3Co4O9.

Enhancement of high temperature thermoelectric performance of cobaltite based materials for automotive exhaust thermoelectric generators

Thermoelectric (TE) generators can directly convert exhaust waste heat into electricity in vehicles. However, the low conversion efficiency of TE generators is the main obstacle to their commercialization in automotive. Their efficiency mainly depends on the performance of the used materials which is quantified by the figure of merit (ZT value). In the present study, single- and co-doped calcium cobaltites (CCO) with rare-earth (Tb) and transition metals (Cu, Fe, Ni, Mn, Cr) were produced using sol–gel technique in order to improve their high temperature TE properties for heat recovery in exhaust manifold applications. By the combined effect of doping approach and the production technique used in this study, a remarkable decrease in the grain size of CCO was obtained, and thus its thermal conductivity dramatically decreased. Besides, thermopower values were improved significantly. The reduction in thermal conductivity and the increase in thermopower led to an enhancement in ZT value of CCO ceramics. Among all the co-doped samples, Tb–Cu co-doped CCO displayed the maximum ZT value of 0.116 at 873 K which is 2.5 times larger than that of pure CCO. The high thermal stability and the enhanced TE performance make Tb–Cu co-doped CCO material a potential candidate for heat recovery in automotive exhaust TE generators.

Controlling the Thermoelectric Properties of Nb-Doped TiO2 Ceramics through Engineering Defect Structures.

Donor-doped TiO2 ceramics are promising high-temperature oxide thermoelectrics. Highly dense (1 - x)TiO2-xNb2O5 (0.005 ≤ x ≤ 0.06) ceramics were prepared by a single-step, mixed-oxide route under reducing conditions. The microstructures contained polygonal-shaped grains with uniform grain size distributions. Subgrain structures were formed in samples with low Nb contents by the interlacing of rutile and higher-order Magnéli phases, reflecting the high density of shear planes and oxygen vacancies. Samples prepared with a higher Nb content showed no subgrain structures but high densities of planar defects and lower concentrations of oxygen vacancies. Through optimizing the concentration of point defects and line defects, the carrier concentration and electrical conductivity were enhanced, yielding a much improved power factor of 5.3 × 10-4 W m-1 K-2 at 823 K; lattice thermal conductivity was significantly reduced by enhanced phonon scattering. A low, temperature-stable thermal conductivity of 2.6 W m-1 K-1 was achieved, leading to a ZT value of 0.17 at 873 K for compositions with x = 0.06, the highest ZT value reported for single Nb-doped TiO2 ceramics without the use of spark plasma sintering (SPS). We demonstrate the control of the thermoelectric properties of Nb-doped TiO2 ceramics through the development of balanced defect structures, which could guide the development of future oxide thermoelectric materials.

Growth and thermoelectric characterization of chalcopyrite ZnSnSb2 with pseudocubic structure

We investigated the growth mechanism and the thermoelectric (TE) properties of the II-IV-V2 group chalcopyrite ZnSnSb2 with a pseudocubic structure, which is a key strategy for improving the TE performance by increasing the degeneracy at the valence band edge. The growth mechanism of ZnSnSb2 shows the peritectic reaction as: ZnSb + SnSb + liquid phase ↔ ZnSnSb2 for 320–360 °C. The ZnSnSb2 single phase was obtained from the starting composition of Zn:Sn:Sb = 1:5:2. The high-temperature TE properties were measured up to 573 K, and the thermal conductivity values were 1.5 times lower than the reported value, which was caused by enhanced phonon scattering by the off-stoichiometric composition. Consequently, the TE figure of merit for off-stoichiometric ZnSnSb2 reached 0.12 at 573 K, which is 1.4 times higher than that of the reported stoichiometric sample.

Processing bulk insulating CaTiO3 into a high-performance thermoelectric material

The development of new high-performance thermoelectric (TE) materials has been garnering significant attention from both the academic communities and industrial fields. Owing to its abundance, eco-friendliness, low cost, and non-toxicity, the oxide CaTiO3 can be considered as a promising high-temperature TE material for large-scale applications. In this regard, this study successfully transformed the insulating CaTiO3 ceramic into a TE material with outstanding TE properties by substituting Ca2+ with La3+ and generating stable oxygen vacancies. The excellent performance of the La-doped samples is mainly attributed to the synergistic effect of La doping and stable oxygen vacancies, which lead to a deeper Fermi energy level and increased density of states. As a result, the power factor was significantly enhanced over a broad temperature range. Coupled with the decreased thermal conductivity resulting from the generated point defects and nano-precipitates to scatter phonons, the desired zT value of 0.4 at 1011 K for bulk Ca0.8La0.2TiO3 was achieved, which was 470% higher than that of pristine bulk CaTiO3. Therefore, our discovery can spark new routes to obtain high-performance TE ceramics and improve their TE performance by introducing dopants and oxygen vacancies.

High thermoelectric figure of merit of porous Si nanowires from 300 to 700\u2009K

Thermoelectrics operating at high temperature can cost-effectively convert waste heat and compete with other zero-carbon technologies. Among different high-temperature thermoelectrics materials, silicon nanowires possess the combined attributes of cost effectiveness and mature manufacturing infrastructures. Despite significant breakthroughs in silicon nanowires based thermoelectrics for waste heat conversion, the figure of merit (ZT) or operating temperature has remained low. Here, we report the synthesis of large-area, wafer-scale arrays of porous silicon nanowires with ultra-thin Si crystallite size of ~4 nm. Concurrent measurements of thermal conductivity (κ), electrical conductivity (σ), and Seebeck coefficient (S) on the same nanowire show a ZT of 0.71 at 700 K, which is more than ~18 times higher than bulk Si. This ZT value is more than two times higher than any nanostructured Si-based thermoelectrics reported in the literature at 700 K. Experimental data and theoretical modeling demonstrate that this work has the potential to achieve a ZT of ~1 at 1000 K.

Selective Enhancement in Phonon Scattering Leads to a High Thermoelectric Figure-of-Merit in Graphene Oxide-Encapsulated ZnO Nanocomposites.

ZnO is a promising candidate for use as an environmentally friendly thermoelectric (TE) material. However, high thermal conductivity leading to a poor TE figure-of-merit (zT) needs to be addressed to achieve a significant TE efficiency for commercial applications. Here, we demonstrate that selective enhancement in phonon scattering leads to an increase in the zT of ZnO because of Al doping and reduced graphene oxide (RGO) encapsulation. These nanocomposites are synthesized via a facile and scalable method. The incorporation of 1 at% Al with 1.5 wt % RGO into ZnO has been found to show significant improvement in zT (0.52 at 1100 K), which is an order of magnitude larger compared to that of bare undoped ZnO. Photoluminescence and X-ray photoelectron spectroscopy measurements confirm that RGO encapsulation significantly quenches surface oxygen vacancies in ZnO along with nucleation of new interstitial Zn donor states. Tunneling spectroscopy performed on bare as well as composite particles reveals that the band gap of ∼3.4 eV for bare ZnO reduces effectively to ∼0.5 eV upon RGO encapsulation, facilitating charge transport. The electrical conductivity also benefits from high densification (>95%) achieved using the spark plasma sintering method, which also aids in reduction of graphene oxide into RGO. The same Al doping and RGO capping synergistically bring about drastic reduction of thermal conductivity, through enhanced interfacial and point-defect-phonon scatterings. These opposing effects on electrical and thermal conductivities lead to enhancement in the power factors as well as the zT value. Overall, a practically viable route has been demonstrated for the synthesis of oxide-RGO TE materials, which could find their potential applications in high-temperature TE power generation.