Thermoelectric properties of SnzCo8Sb24 skutterudites

Sn-filled CoSb₃ skutterudite compounds were synthesized by the induction melting process. Formation of a single δ-phase of the synthesized materials was confirmed by X-ray diffraction analysis. The temperature dependences of the Seebeck coefficient, electrical resistivity and thermal conductivity were examined in the temperature range of 300-700 K. Positive Seebeck and Hall coefficients confirmed p-type conductivity. Electrical resistivity increased with increasing temperature, which shows that the Sn-filled CoSb₃ skutterudite is a degenerate semiconductor. The thermal conductivity was reduced by Sn-filling because the filler atoms acted as phonon scattering centers in the skutterudite lattice. The lowest thermal conductivity was achieved in the composition of Sn_0.25Co₈Sb₂₄.     

Theory of hot-electron quantum diffusion in semiconductors

In the linear response regime close to equilibrium, the fluctuation-dissipation theorem relates linear transport coefficients via the well-known Green–Kubo or Einstein relation. The latter embodies a deep connection between fluctuations causing diffusion and dissipation, which are responsible for a finite mobility. Far from equilibrium, however, the Einstein relation is no longer valid so that both the mobility and diffusivity gain their own physical integrity. Consequently, beyond a linear response, both quantities have to be described by different approaches. Unfortunately, there is a strong imbalance of research activities devoted to the study of both transport mechanisms in semiconductors. On one hand, the rich physics of high-field quantum drift in semiconducting structures has a long history and has reached a high level of sophistication. On the other hand, there are only comparatively few and unsystematic studies that cover quantum diffusion of carriers under high-field conditions. This review aims at reducing this gap by presenting a unified approach to quantum drift and quantum diffusion. Starting from a semi-phenomenological basis, a quantum theory of transport coefficients is developed for one- as well as multi-band models. Physical implications are illustrated by selected applications whereby the quantum character of the approach is emphasized. Furthermore, the basic unified treatment of transport coefficients is extended by accounting for the two-time dependence of one-particle correlation functions in quantum statistics. As an application, a phononless transport mechanism is identified, which solely originates from the double-time nature of the evolution. Finally, additional examples are presented that illustrate the important role played by quantum diffusion in semiconductor physics.     

The effect of titanium diboride addition on the thermoelectric properties of β-FeSi2 semiconductors

β-FeSi₂-TiB₂ composites with various amounts of TiB₂, from 0 up to 30 vol%, were prepared by hot pressing. The electrical and thermal conductivities, and the Seebeck coefficient were measured as a function of temperature. The results show that the thermal and electrical transport behavior of the composites is different as the volume fraction of TiB₂ is below and above about 0.255. A 5 vol% TiB₂ added sample has higher figure of merit than one without TiB₂ for temperatures above 650 K. The influence of an additional phase, ε-FeSi, formed during the hot pressing, on the thermoelectric properties of the β-FeSi₂-TiB₂ composites was also discussed.     

Non-monotonic thermoelectric behavior of lead telluride in quantum‐well‐like structures

Transport coefficients of quantum‐well‐like structures may in special circumstances show several interesting features. We have obtained theoretical expressions for transport coefficients including Lorenz factor and Seebeck coefficient in well-like structures taking into account the contributions from various sub-bands. Calculations based on the model have been presented for lead telluride quantum wells of varying well width (a). The results indicate a significant deviation in the transport behaviour as compared to the bulk particularly for a<100 nm. Unlike in the bulk material changes in Lorenz factors are rather less pronounced and at a=10 nm it is virtually a constant at 2.0. The Seebeck coefficient on the other hand shows a sharp rise below 100 nm. This region may be of particular interest in thermoelectric device applications. The results show an unusual behaviour of the Lorenz factor and Seebeck coefficient below a 100 nm well width. Moreover, contributions from quantized sub‐bands occupied up to the Fermi level may under certain conditions lead to a non-monotonic behavior which is also reported in some recent experimental measurements on particular PbTe quantum well structures.     

Parallel syntheses and thermoelectric properties of Ce-doped SrTiO3 thin films

Thermoelectric properties of single crystalline Ce_xSr_1−xTiO₃ films (0 ≤ x ≤ 0.5) have been studied by using combinatorial pulsed-laser deposition. Temperature gradient method was used for identifying an optimum growth temperature for SrTiO₃ homoepitaxial growth, at which both oxygen stoichiometry and persisting layer-by-layer growth mode could be accomplished. Electrical conductivity (σ) and Seebeck coefficient (S) were measured at room temperature for the composition-spread films grown at the optimized temperature and found to be considerably higher than those reported for bulk poly-crystalline compounds. Hall measurement revealed that carrier density linearly increased with increasing x, suggesting that a trivalent Ce ions substituted divalent Sr ions to supply electrons. A maximum power factor (S²σ) was obtained for the x = 0.2 film, being 7 and 14 μW/K² cm at 300 and 900 K, respectively.     

Synthesis, crystal structure and thermoelectric properties of IrSn1.5Te1.5 -based skutterudites

The mixed anion skutterudite IrSn_1.5Te_1.5 has been synthesized and characterized by X-ray powder diffraction, thermopower and electrical resistivity measurements. Structural analysis reveals that Sn and Te order in layers perpendicular to the [111] direction of the skutterudite unit cell, and a distortion of the anion sublattice is evident. The thermopower (S) is 160 μV/K at room temperature, while the electrical resistivity (ρ) is . The effects of chemical substitutions on the Ir site (Ru, Pd) and Sn site (In, Sb) have been investigated. The power factor (S²/ρ) was found to improve with In substitution but, at 0.9 μW/K² cm, is too small for this material to be useful for thermoelectric applications.     

Electrical and structural properties of Ce0.9CoFe3Sb12 thermoelectric thin films

In this work, we show experimental results for growth conditions of thermoelectric Ce_0.9CoFe₃Sb₁₂ thin films. An rf-magnetron sputtering system has been used to grow the films on single crystal substrates of sapphire (Al₂O₃), silicon (Si), and magnesium oxide (MgO) at different substrate temperatures between 250 and 450 °C. The films were thermoelectrically characterized with resistivity and thermopower measurements as functions of temperature. The results show linear behavior of resistivity with temperature, and thermopower growth with the temperature increase. Such behavior is typical for metallic materials. The structure and surface morphology of the samples were analyzed by X-ray diffraction pattern and atomic force microscopy (AFM), respectively.     

Large enhancement of the thermoelectric Seebeck coefficient for amorphous oxide semiconductor superlattices with extremely thin conductive layers

Herein we demonstrate that amorphous oxide semiconductor (AOS) superlattices composed of a‐In–Zn–O (well) and a‐In–Ga–Zn–O (barrier) layers, fabricated on SiO₂ glass substrate by pulsed laser deposition at room temperature, exhibited an enhanced Seebeck coefficient |S |. The |S | value increases drastically with decreasing a‐In–Zn–O thickness (d_IZO) when d_IZO < ∼5 nm, and reached 73 µV K^–1 (d_IZO = 0.3 nm), which is ∼4 times larger than that of bulk |S |_3D (19 µV K^–1), while it kept its high electrical conductivity, clearly demonstrating that the quantum size effect can be utilized in AOS superlattices. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Phase transitions investigation in ZnTe by thermoelectric power measurements at high pressure

The pressure-induced phase transitions were studied in ZnTe by the thermoelectric power (S) technique. For the high-pressure trigonal phase P3₁21 cinnabar the large thermopower values S≈+400 correspond to semiconductor hole conductivity. During a transition into the orthorhombic structure Cmcm the value of S dropped by 40-50 times indicating metallic hole conductivity, like in the high pressure phases of other chalcogenides of II Group (HgSe, HgTe, CdTe) with Cmcm structure. In a transient region between the trigonal and orthorhombic phase (especially under decreasing pressure) a novel phase has been observed with a negative value of S. By analogy with other Zn and Cd chalcogenides whose NaCl phases have an electron type of conductivity the phase observed may have a NaCl structure.     

The transport properties in Nd0.75Sr1.25CoO4 film: Evidence for polaronic transport

The experiments of electrical resistivity and thermopower on Nd_0.75Sr_1.25CoO₄ film in the temperature range 90 K<T<310 K were carried out. The great difference in the activation energies estimated from thermopower and resistivity, a characteristic of small polarons, is observed, providing strong evidence for polaron-dominated transport mechanism in this material. Furthermore, the activation energy at intermediate-temperature region is larger than that at low-temperature region in resistivity, but it is not observed in thermopower, indicating that the energy for the creation of the carriers is slightly lower at low-temperature region than that at intermediate-temperature region. At the same time, the abrupt drop in the thermopower and the abnormal peak in the differential curve of resistivity indicate that a phase transition between a paramagnetic state and a ferromagnetic state occurs at temperature about 218 K. The positive thermopower in the whole temperature range measured suggests that the carriers are holes in this system.     

Combinatorial synthesis and high throughput evaluation of thermoelectric power factor in Mg-Si-Ge ternary compounds

Discrete phase libraries of thermoelectric compounds, Mg_xSi_yGe_1−y, were fabricated by a combinatorial pulsed laser deposition followed by annealing as a thin film form on an integrated ceramic substrate. In the substrate are embedded four probe electrical contacts to each sample, lead wires and pads to be accessed by needle probes. Resistivity and Seebeck coefficient were evaluated electrically, while temperature difference was locally given to each sample by a local heater also embedded in the substrate. The sample temperature (300-673 K) was controlled by a heating stage and temperature difference at the two contact points for each sample was evaluated by an infrared camera. The dependences of polarity and absolute values of Seebeck coefficient on the composition agree well with the data in literature.     

The large anisotropy of the magnetic and transport properties in the Ba5Co5ClO13 single crystal

In this Letter, the single crystals of Ba₅Co₅ClO₁₃ were grown by the flux method successfully. Their structure, magnetic and transport properties were studied. A large anisotropy of the magnetic and transport properties has been detected in this compound. Below the TN∼108 K, the magnetic susceptibility exhibits an antiferromagnetic peak in χc and an upturn transition in χab. We suggest that this behavior is consistent with the competition of the ferromagnetic (FM) intra-blocks coupling and antiferromagnetic (AFM) inter-blocks coupling in this compound. The temperature dependence of the resistivity displays a hump in ρab and a kink in ρc around TN, suggesting the strong coupling between the transport and magnetic properties. Above and below the transition, the transport properties in ab plane follow the three-dimensional (3D) variable range hopping (VRH) mechanism.     

Large Seebeck coefficients in iron‐oxypnictides: a new route towards n‐type thermoelectric materials

The iron‐oxypnictide compounds, recently reported as a new class of superconductors when appropriately doped, exhibit large Seebeck coefficients, of the order of –100 µV/K, while keeping good electrical conductivity. Their power factor shows a peak at low temperatures, suggesting possible applications of these materials in thermoelectric cooling modules in the liquid nitrogen temperature range. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Thermal and thermoelectric behavior of silicon-germanium quantum well structures

Tailoring thermoelectric materials for specific designs and applications has been gaining momentum during past three decades. Initially confined to conventional (bulk) framework an entirely new scenario emerged with inclusion of low-dimensional structures in the scheme of things. The paper examines the effect of size reduction on phonon and electron properties in two-dimensional (quantum well) structures with an aim to maximize thermoelectric performance. The formulation has been applied to silicon-germanium quantum wells with well width ranging from 50–500 ? aimed at finding best alloy combination for thermoelectric applications.     

Improvement of transport properties for polycrystalline silicon prepared by plasma-enhanced chemical vapor deposition

The carrier transport property of polycrystalline silicon (poly-Si:H:F) thin films was studied in relation to film microstructure, impurity, in situ or post-annealing treatments to obtain better carrier transport properties. Poly-Si:H:F films were prepared from SiF₄ and H₂ gas mixtures at temperatures <300 °C. Dark conductivity of the films prepared at high SiF₄/H₂ gas flow ratio (e.g., 60/3 sccm) exhibits a high value for intrinsic silicon and its Fermi level is located near the conduction band edge. The carrier incorporation is suppressed well, either by in situ hydrogen plasma treatment or by post-annealing with high-pressure hot-H₂O vapor. It is confirmed that weak-bonded hydrogen atoms are removed by the hot-H₂O vapor annealing. In addition, evident correlation between impurity concentrations and dark conductivity is not found for these films. It is thought that the carrier incorporation in the films prepared at high SiF₄/H₂ gas flow ratios is related to grain-boundary defects such as weak-bonded hydrogen. By applying hot-H₂O vapor annealing at 310 °C to a 1-μm-thick p-doped (400)-oriented poly-Si:H:F film, Hall mobility was improved from 10 cm²/Vs to 17 cm²/Vs. Received: 7 August 2000 / Accepted: 2 March 2001 / Published online: 20 June 2001     

Structure and electrical transport properties of bismuth thin films prepared by RF magnetron sputtering

Bismuth thin films were prepared on glass substrates with RF magnetron sputtering and the effects of deposition temperature on surface morphology and their electrical transport properties were investigated. Grain growth of bismuth and the coalescence of grains were observed above 393 K with field emission secondary electron microscopy. Continuous thin films could not be obtained above 448 K because of the segregation of grains. Hall effect measurements showed that substrate heating yields the decrease of carrier density and the increase of mobility in exponential ways until 403 K. Resistivity of sputter deposited bismuth films has its minimum (about 0.7 × 10⁻³ Ω cm) in range of 403-433 K. Annealing of bismuth films deposited at room temperature was carried out in a radiation furnace with flowing hydrogen gas. The change of resistivity was not significant due to the cancellation of the decrease of carrier density and the increase of mobility. However, the abrupt change of electrical properties of film annealed above 523 K was observed, which is caused by the oxidation of bismuth layer.     

Nanostructured thermoelectric oxides with low thermal conductivity

Complex metal oxides, such as e.g. perovskite‐type phases are developed as potential functional materials to improve the efficiency of thermoelectric converters. Among those, cobaltates with p‐type conductivity and n‐type manganates are considered for the realisation of a ceramic thermoelectric converter. Sintered pellets with the composition AMO_3–δ (A = Ln, RE; M = Co, Mn, Ni, Ti) and “Ca₃Co₄O₉ derivates” were synthesized and characterised concerning their thermoelectric properties in a broad temperature range. It was found that the Seebeck coefficient and the electrical conductivity do not depend on the dimensions of the crystallites, while the heat conductivity can be substantially lowered by decreasing the size of the crystalline domains in these systems. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

X-ray photoelectron spectroscopy study and thermoelectric properties of Al-doped ZnO thin films

In this paper, high quality Al-doped ZnO (AZO) thin films were prepared by direct current (DC) reactive magnetron sputtering using a Zn target (99.99%) containing Al of 1.5 wt.%. The films obtained were characterized by X-ray photoelectron spectroscopy (XPS) and thermoelectric measurements. The XPS results reveal that Zn and Al exist only in oxidized state, while there are dominant crystal lattice and rare adsorbed oxygen for O in the annealed AZO thin films. The studies of thermoelectric property show a striking thermoelectric effect in the AZO thin films. On the one hand, the thermoelectromotive and magnetothermoelectromotive forces increase linearly with increasing temperature difference (ΔT). On the other hand, the thermoelectric power (TEP) decreases with the electrical resistance of the sample. But the TEP increases with the increase of temperature below 300 K, and it nearly does not change around room temperature. The experimental results also demonstrate that the annealing treatment increases TEP, while the external magnetic field degrades TEP.     

Quantum transport in randomly diluted quantum percolation clusters in two dimensions

We study the hopping transport of a quantum particle through finite, randomly diluted percolation clusters in two dimensions. We investigate how the transmission coefficient T behaves as a function of the energy E of the particle, the occupation concentration p of the disordered cluster, the size of the underlying lattice, and the type of connection chosen between the cluster and the input and output leads. We investigate both the point-to-point contacts and the busbar type of connection. For highly diluted clusters we find the behavior of the transmission to be independent of the type of connection. As the amount of dilution is decreased we find sharp variations in transmission. These variations are the remnants of the resonances at the ordered, zero-dilution, limit. For particles with energies within 0.25≤E≤1.75 (relative to the hopping integral) and with underlying square lattices of size 20×20, the configurations begin transmitting near p_α=0.60 with T against p curves following a common pattern as the amount of dilution is decreased. Near p_β=0.90 this pattern is broken and the transmission begins to vary with the energy. In the asymptotic limit of very large clusters we find the systems to be totally reflecting in almost all cases. A few clear exceptions we find are when the amount of dilution is very low, when the particle has energy close to a resonance value at the ordered limit, and when the particle has energy at the middle of the band. These three cases, however, may not exhaust all possible exceptions.