Electrical Transport Properties of Filled CoSb<Subscript>3</Subscript> Skutterudites: A Theoretical Study

We present an investigation of electronic structures and electrical transport properties of some filled CoSb₃ skutterudites by combining ab initio projected augmented plane-wave calculations and Boltzmann transport theory with electron group velocity evaluated by the momentum matrix method. The systems are studied in a 2 × 2 × 2 supercell of Co₄Sb₁₂ to reveal the effects induced by different filler atoms and their filling fractions. The temperature dependences of the Seebeck coefficient and power factor are studied, and they are in good agreement with experimental data. Our results reveal an optimal filling fraction for n-type filled CoSb₃ skutterudites and related compounds for achieving the highest power factor values.     

Molecular Dynamics Simulation on Mechanics of Skutterudite CoSb<Subscript>3</Subscript> Nanowire

For the binary thermoelectric material CoSb₃ with a complex crystal structure, the Morse potential functional form is employed to describe its three-dimensional atomic interactions. The mechanical responses and deformation behavior of a rectangular cross-section CoSb₃ nanowire subjected to uniaxial tensile strain are simulated at constant temperature by the molecular dynamics method. The deformation is strain controlled with constant strain rate. When the strain increases, necking gradually becomes distinct near the middle of the model, and complete damage occurs at around 60% strain. The single-crystal CoSb₃ nanowire exhibits properties distinct from those of single-crystal CoSb₃ bulk previously studied. Comparison of the stress–strain curves and configuration evolutions of the CoSb₃ nanowire and bulk during tensile loading indicate that an interesting brittle–ductile transition phenomenon occurs when the single-crystal CoSb₃ varies from bulk to nanowire. Future efforts should be devoted to seeking the critical dimension at which this transition happens and the mechanism behind it.     

Effect of Cyclic Thermal Loading on the Microstructure and Thermoelectric Properties of CoSb<Subscript>3</Subscript>

The effect of cyclic thermal loading on the microstructure and thermoelectric properties of CoSb₃ was investigated. The microstructures of the samples were characterized by x-ray diffractometry, scanning electron microscopy, energy dispersive x-ray spectrometry and density measurements. The electrical conductivity, the Seebeck coefficient and the thermal conductivity were measured from room temperature to 800 K. Under cyclic thermal loading, antimony partially volatilized from the surface of the sample, and the density obviously decreased. After 2000 cycles, the phase composition of the sample remained stable, and the average grain size did not change significantly. Moreover, the electrical conductivity varied only slightly, except in the low temperature region. The Seebeck coefficient decreased slightly. However, the thermal conductivity changed remarkably with increasing numbers of thermal cycles.     

Influence of Group IV-Te Alloying on Nanocomposite Structure and Thermoelectric Properties of Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> Compounds

Thermoelectric compounds based on doped bismuth telluride and its alloys have recently attracted increasing interest. Due to their structural features they show increased values of the thermoelectric figure of merit (ZT). A promising approach to improve the thermoelectric properties is to manufacture nanocomposite materials exhibiting lower thermal conductivities and higher ZT. The ZT value of compounds can be shifted reasonably to higher values (>1) by alloying with IV-Te materials and adequate preparation methods to form stable nanocomposites. The influence of PbTe and Sn on the thermoelectric properties is studied as a function of concentration and preparation methods. Melt spinning and spark plasma sintering were applied to form nanocomposite materials that were mechanically and thermodynamically stable for applications in thermoelectric devices. The structural properties are discussed based on analysis by transmission electron microscopy and x-ray diffraction.     

Thermoelectric Properties of NdGd<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript>3</Subscript> Prepared by CS<Subscript>2</Subscript> Sulfurization

Ternary rare-earth sulfides NdGd_1+x S₃, where 0 ≤ x ≤ 0.08, were prepared by sulfurizing Ln₂O₃ (Ln = Nd, Gd) with CS₂ gas, followed by reaction sintering. The sintered samples have full density and homogeneous compositions. The Seebeck coefficient, electrical resistivity, and thermal conductivity were measured over the temperature range of 300 K to 950 K. All the sintered samples exhibit a negative Seebeck coefficient. The magnitude of the Seebeck coefficient and the electrical resistivity decrease systematically with increasing Gd content. The thermal conductivity of all the sintered samples is less than 1.9 W K⁻¹ m⁻¹. The highest figure of merit ZT of 0.51 was found in NdGd_1.02S₃ at 950 K.     

High electric-field-induced strain beahvior of single-crystal Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>-xPbTiO<Subscript>3</Subscript> multilayer piezoelectric actuators

Two 10-mm-long multilayer prototype actuators were fabricated by a stack method using 55 pieces of 5 mm×5 mm×0.15 mm Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃ (PMNT) single crystals and PZT-5A ceramics, respectively. The strain values for PMNT multilayer piezoelectric actuators are twice those of PZT-5A multilayer actuators, and 20.8-μm displacements can be achieved at the same E-field of 15 kV/cm. Although thermal and electrical history markedly impact dielectric and piezoelectric performance of PMNT crystals, the PMNT multilayer actuator can still achieve large displacements with approximately linear behavior below 60°C. Broad stable dynamic displacement characteristic and fast displacement response make the new-type actuators promising candidates for the application in new-generation high-performance solid-state actuators.     

Microstructure and Characteristics of Thin-Film La<Subscript>0.8</Subscript>Sr<Subscript>0.2</Subscript>Co<Subscript>0.5</Subscript>Ni<Subscript>0.5</Subscript>O<Subscript>3</Subscript>/ZnO:Al Heterocontact CO Sensors Prepared by RF Magnetron Sputtering

Highly sensitive CO gas sensors based on heterocontacts of ZnO:Al on La_0.8Sr_0.2Co_0.5Ni_0.5O₃ (LSCNO) were fabricated successfully. La_0.8Sr_0.2Co_0.5Ni_0.5O₃ thin films were coated on (100) silicon wafers by a sol-gel method including the Pechini process followed by a spin-coating procedure. Then, ZnO:Al films prepared by radiofrequency (RF) magnetron sputtering at various oxygen partial pressures and deposited on as-deposited La_0.8Sr_0.2Co_0.5Ni_0.5O₃ films were investigated. The results revealed that the CO sensing ability of the film prepared with the ratio of O₂/Ar = 5/5 (ratio of volume flow rate) was the worst, owing to the highest (002) plane orientation in the ZnO:Al film. In contrast, the ZnO:Al film prepared with O₂/Ar = 3/7 exhibited better CO sensitivity. Furthermore, all two-layer samples showed higher CO sensitivities than single-layer samples. The CO sensitivity of ZnO:Al/La_0.8Sr_0.2Co_0.5Ni_0.5O₃ thin film was 45% for 500 ppm CO at a sensing temperature of 200°C.     

Effect of Rapid Thermal Annealing on Sputtered CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> Thin Films

Calcium copper titanium oxide (CaCu₃Ti₄O₁₂, abbreviated to CCTO) films were deposited on Pt/Ti/SiO₂/Si substrates at room temperature (RT) by radiofrequency magnetron sputtering. As-deposited CCTO films were treated by rapid thermal annealing (RTA) at various temperatures and in various atmospheres. X-ray diffraction patterns and scanning electron microscope (SEM) images demonstrated that the crystalline structures and surface morphologies of CCTO thin films were sensitive to the annealing temperature and ambient atmosphere. Polycrystalline CCTO films could be obtained when the annealing temperature was 700°C in air, and the grain size increased signifi- cantly with annealing in O₂. The 0.8-μm CCTO thin film that was deposited at RT for 2 h and then annealed at 700°C in O₂ exhibited a high dielectric constant (ε′) of 410, a dielectric loss (tan δ) of 0.17 (at 10 kHz), and a leakage current density (J) of 1.28 × 10⁻⁵ A/cm² (at 25 kV/cm).     

Superior suppression of gate current leakage in Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Si<Subscript>3</Subscript>N<Subscript>4</Subscript> bilayer-based AlGaN/GaN insulated gate heterostructure field-effect transistors

AlGaN/GaN-based metal-insulator-semiconductor heterostructure field-effect transistors (MIS-HFETs) with Al₂O₃/Si₃N₄ bilayer as insulator have been investigated in detail, and compared with the conventional HFET and Si₃N₄-based MIS-HFET devices. Al₂O₃/Si₃N₄ bilayer-based MIS-HFETs exhibited much lower gate current leakage than conventional HFET and Si₃N₄-based MIS devices under reverse gate bias, and leakage as low as 1×10⁻¹¹ A/mm at −15 V has been achieved in Al₂O₃/Si₃N₄-based MIS devices. By using ultrathin Al₂O₃/Si₃N₄ bilayer, very high maximum transconductance of more than 180 mS/mm with ultra-low gate leakage has been obtained in the MIS-HFET device with gate length of 1.5 μm, a reduction less than 5% in maximum transconductance compared with the conventional HFET device. This value was much smaller than the more than 30% reduction in the Si₃N₄-based MIS device, due to the employment of ultra-thin bilayer with large dielectric constant and the large conduction band offset between Al₂O₃ and nitrides. This work demonstrates that Al₂O₃/Si₃N₄ bilayer insulator is a superior candidate for nitrides-based MIS-HFET devices.     

Memory Effect of Metal-Insulator-Silicon Capacitor with HfO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Multilayer and Hafnium Nitride Gate

Metal-insulator-silicon capacitors have been fabricated using novel insulators of SiO₂/HfO₂-Al₂O₃-HfO₂ (HAH)/Al₂O₃ and metallic HfN gate, exhibiting a program-erasable characteristic. The memory capacitor presents a large memory window of 2.4 V under +12 V program/–14 V erase for 10 ms, no erase saturation, and sufficient electron- and hole-trapping efficiencies such as an electron density of ∼7 × 10¹² cm^–2 under 13 V program for 0.5 ms and a hole density of ∼4 × 10¹² cm^–2 under –12 V erase for 0.5 ms. The observed properties are attributed to the introduction of high permittivity atomic-layer-deposited HAH/Al₂O₃ as well as high work function HfN gate. The related mechanism is addressed accordingly.     

Superconducting and Transport Properties of (Bi-Pb)-Sr-Ca-Cu-O with Nano-Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> Additions

The effect of nano Cr₂O₃ additions in (Bi, Pb)-Sr-Ca-Cu-O superconductors using the coprecipitation method is reported. Nano Cr₂O₃ with 0.1, 0.3, 0.5, 0.7, and 1.0 wt.% were added to the (Bi, Pb)-Sr-Ca-Cu-O system. The critical temperature (T _c) and transport critical current density (J _c) were determined by the four-point probe technique. The phases in the samples were determined using the powder X-ray diffraction method. The microstructure was observed by a scanning electron microscope and the distribution of nano Cr₂O₃ was determined by energy-dispersive X-ray analysis (EDX). The maximum T _c and J _c were observed for the sample with 0.1 wt.% nano Cr₂O₃. The variation in the J _c of all the samples was explained by the effective flux pinning by nano Cr₂O₃ in the samples. Using the self-field approximation together with the dependence of J _c on temperature, the characteristic length (L _c) associated with the pinning force was estimated to be approximately the same as the average grain size in all the samples.     

Memory Switching Characteristics in Amorphous Ga<Subscript>2</Subscript>Se<Subscript>3</Subscript> Films

Ga₂Se₃ films were deposited by the thermal evaporation of the bulk material onto pyrographite substrates under vacuum. The I–V characteristic curves were found to be typical for a memory switch. They exhibited a transition from an ohmic region in the lower-field region to a non-ohmic region in the high-field region in the preswitching region, which has been explained by the Poole–Frenkel effect. The temperature dependence of the resistance in the ohmic region was found to be that of a thermally activated process. It was also found that the mean value of the switching voltage increased linearly with increasing film thickness in the range from 291 nm to 516 nm, while it decreased exponentially with increasing temperature in the range from 298 K to 393 K. The results were explained in accordance with the electrothermal model for the switching process.     

Synthesis and Thermoelectric Properties of “Nano-Engineered” CoSb<Subscript>3</Subscript> Skutterudite Materials

Because of their good electrical transport properties, skutterudites have been widely studied as potential next-generation thermoelectric (TE) materials. One of the main obstacles to further improving their thermoelectric performance has been reducing their relatively high thermal conductivity. To some extent, this hindrance has been partially resolved by filling the voids found in the skutterudite structure with so-called “rattling” atoms. It has been predicted that reducing the dimensionality in a TE material would have a positive effect in enhancing its thermoelectric properties, for example increasing the thermopower and reducing the thermal conductivity. Introducing nanoparticles into the skutterudite materials could therefore have favorable effects on their electrical properties and should also reduce lattice thermal conductivity by introducing extra scattering centers throughout the sample. Nanoparticles may also be used in conjunction with void filling for further reduction of the thermal conductivity of skutterudites. Cobalt triantimonide (CoSb₃) samples with different amounts of embedded nanoparticles have been grown, and the electrical and thermal transport properties for these composites have been measured from 10 K to 650 K. The synthetic techniques and electrical and thermal transport data are discussed in this paper.     

Thermoelectric Properties of Ca-Filled CoSb<Subscript>3</Subscript>-Based Skutterudites Synthesized by Mechanical Alloying

Ca _z Co_4−x (Fe/Mn) _x Sb₁₂ skutterudites were prepared by mechanical alloying and hot pressing. The phases of mechanically alloyed powders were identified as γ-CoSb₂ and Sb, but they were transformed to δ-CoSb₃ by annealing at 873 K for 100 h. All specimens had a positive Hall coefficient and Seebeck coefficient, indicating p-type conduction by holes as majority carriers. For the binary CoSb₃, the electrical conductivity behaved like a nondegenerate semiconductor, but Ca-filled and Fe/Mn-doped CoSb₃ showed a temperature dependence of a degenerate semiconductor. While the Seebeck coefficient of intrinsic CoSb₃ increased with temperature and reached a maximum at 623 K, the Seebeck coefficient increased with increasing temperature for the Ca-filled and Fe/Mn-doped specimens. Relatively low thermal conductivity was obtained because fine particles prepared by mechanical alloying lead to phonon scattering. The thermal conductivity was reduced by Ca filling and Fe/Mn doping. The electronic thermal conductivity was increased by Fe/Mn doping, but the lattice thermal conductivity was decreased by Ca filling. Reasonable thermoelectric figure-of-merit values were obtained for Ca-filled Co-rich p-type skutterudites.     

Microstructure and Thermoelectric Properties of <Emphasis Type="Italic">n</Emphasis>- and <Emphasis Type="Italic">p</Emphasis>-Type Doped Mg<Subscript>2</Subscript>Sn Compounds Prepared by the Modified Bridgman Method

Mg₂Sn compounds were prepared by the modified vertical Bridgman method, and were doped with Bi and Ag to obtain n- and p-type materials, respectively. Excess Mg was also added to some of the ingots to compensate for the loss of Mg during the preparation process. The Mg₂Sn samples were characterized by x-ray diffraction (XRD) and scanning electron microscopy (SEM), and their power factors were calculated from the Seebeck coefficient and electrical conductivity, measured from 80 K to 700 K. The sample prepared with 4% excess Mg, which contains a small amount of Mg₂Sn + Mg eutectic phase, had the highest power factor of 12 × 10⁻³ W m⁻¹ K⁻² at 115 K, while the sample doped with 2% Ag, in which a small amount of eutectics also exists, has a power factor of 4 × 10⁻³ W m⁻¹ K⁻² at 420 K.     

Microwave Dielectric Properties of ZnO-2TiO<Subscript>2</Subscript>-Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> Ceramics with BaCu (B<Subscript>2</Subscript>O<Subscript>5</Subscript>) Addition

The influence of BaCu(B₂O₅) (BCB) addition on the sintering temperature and microwave dielectric properties of ZnO-2TiO₂-Nb₂O₅ (ZTN) ceramic has been investigated using dilatometry, x-ray diffraction, scanning electron microscopy, and microwave dielectric measurements. A small amount of BCB addition to ZTN can lower the sintering temperature from 1100°C to 900°C. The reduced sintering temperature was attributed to the formation of the BCB liquid phase. The ZTN ceramics containing 3.0 wt.% BCB sintered at 900°C for 2 h have good microwave dielectric properties of Q × f = 19,002 GHz (at 6.48 GHz), ε _r = 45.8 and τ _f  = 23.2 ppm/°C, which suggests that the ceramics can be applied in multilayer microwave devices, provided that Ag compatibility exists.     

Thickening kinetics of interfacial Cu<Subscript>6</Subscript>Sn<Subscript>5</Subscript> and Cu<Subscript>3</Subscript>Sn layers during reaction of liquid tin with solid copper

Thickening behavior of interfacial η (Cu₆Sn₅) phase and ɛ (Cu₃Sn) phase intermetallic layers was investigated in liquid tin/solid copper reaction couples over reaction times from 30 sec to over 4,000 min and temperatures from 250°C to 325°C. A scanning electron microscope (SEM) was used to quantify the interfacial microstructure at each processing condition. The η developed with a scalloped morphology, while the ɛ always grew as a somewhat undulated planar layer in phase with the η. The thickness of each phase was quantitatively evaluated from SEM micrographs using imaging software. Thickening kinetics of the ɛ and η compounds were modeled using time- and temperature-dependent empirical power-law equations. From the model, values for the kinetic exponent, rate constant, and activation energy were established for each intermetallic layer. Measured values for the kinetic exponents and activation energies suggest that thickening of the η is controlled by a grain-boundary diffusion mechanism, and growth of the ɛ occurs by solid-state diffusion, probably grain-boundary diffusion.     

Effect of partial la filling on high-temperature thermoelectric properties of IrSb<Subscript>3</Subscript>-based skutterudite compounds

We previously reported that IrSb₃-based ternary compounds showed good electrical properties and that relatively high thermal conductivity prevented the enhancement of the efficiency of these compounds.¹ Recently, we have investigated the high-temperature thermoelectric properties of La-filled IrSb₃-based skutterudite compounds from the viewpoint of a decrease in lattice thermal conductivity. It has been confirmed from Rietveld analysis that the La ions are partially placed in cages of La-filled and Ge-charge-compensated La_YIr₄Ge_3YSb_12−3Y compounds and 53% filling of La ions is obtained. Owing to the rattling effect of La ions in cages, the La-filled and Ge-charge-compensated La_YIr₄Ge_3YSb_12−3Y compounds exhibit tremendously decreased lattice thermal conductivity at room temperature, 1.8 W/mK from 10.2 W/mK of binary IrSb₃.     

Electronic Structures and Transport Properties of Single-Filled CoSb<Subscript>3</Subscript>

Band structure and density of states (DOS) of CoSb₃ single-filled by seven kinds of atoms (R_0.125Co₄Sb₁₂) are calculated by the density functional method. The results for the electronic structures in turn determine the electrical transport and thermal performance. It is found that the band structure of R_0.125Co₄Sb₁₂ shows no significant changes compared with that of CoSb₃, and the results indicate that void filling with a small quantity of R atoms does not change the bond formation in CoSb₃. However, the partial DOS reveals that there could be interaction of Sn, Tl, In, and Yb atoms with CoSb₃. The results for the electrical transport properties and thermal properties show that Sn, Tl, and In atoms increase the Seebeck coefficient and La, Eu, and Yb atoms are helpful for increasing the electron concentration and decreasing the thermal conductivity further. According to our calculations and Yang’s principle, double-filled CoSb₃ with atomic combinations of (In, Ca), (In, Ba), (Sn, Eu), and (Sn, La) may exhibit good thermoelectric performance.     

Low-Cycle Fatigue Properties of CoSb<Subscript>3</Subscript>-Based Skutterudite Compounds

An experimental study was carried out on CoSb₃-based skutterudites. Tests were carried out at room temperature and in air. Firstly, static compression tests were conducted to determine the compressive strength of the materials. Then stress-controlled low-cycle fatigue tests were performed using a sinusoidal waveform of constant amplitude. The influence of the maximum stress on fatigue life was analyzed. The surfaces and fracture surfaces of the specimens were observed by scanning electron microscopy. Fatigue crack initiation was observed to occur from pre-existing defects in the specimen surface, and the fatigue fracture surface showed intergranular fracture behavior. Finally, interrupted low-cycle fatigue tests were conducted to analyze residual strength degradation.