Thermoelectric Properties of Mo<Subscript>3</Subscript>Sb<Subscript>5.4</Subscript>Te<Subscript>1.6</Subscript> and Ni<Subscript>0.06</Subscript>Mo<Subscript>3</Subscript>Sb<Subscript>5.4</Subscript>Te<Subscript>1.6</Subscript>

Mo₃Sb₇, crystallizing in the Ir₃Ge₇ type structure, has poor thermoelectric (TE) properties due to its metallic behavior. However, by a partial Sb-Te exchange, it becomes semiconducting without noticeable structure changes and so achieves a significant enhancement in the thermopower with the composition of Mo₃Sb₅Te₂. Meanwhile, large cubic voids in the Mo₃Sb₅Te₂ crystal structure provide the possibility of filling the voids with small cations to decrease the thermal conductivity by the so-called rattling effect. As part of the effort to verify this idea, we report herein the growth as well as measurements of the thermal and electrical transport properties of Mo₃Sb_5.4Te_1.6 and Ni_0.06Mo₃Sb_5.4Te_1.6.     

Low-Temperature Transport Properties of Sn<Subscript>24</Subscript>P<Subscript>19.3</Subscript>Br<Subscript>8</Subscript> and Sn<Subscript>17</Subscript>Zn<Subscript>7</Subscript>P<Subscript>22</Subscript>Br<Subscript>8</Subscript>

We report on temperature-dependent thermal conductivity, resistivity, and Seebeck coefficient of two polycrystalline Br-containing Sn-clathrate compounds with the type I crystal structure. Interstitial Br atoms reside inside the polyhedral cavities formed by the framework, resulting in hole conduction. The framework bonding directly influences the transport properties of these two compositions. The transport properties of these two clathrates are compared with those of other Sn-clathrates. We also discuss our results in terms of the potential for thermoelectric applications.     

Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>-Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript> Superlattices Grown by Nanoalloying

In this work, Bi₂Te₃-Sb₂Te₃ superlattices were prepared by the nanoalloying approach. Very thin layers of Bi, Sb, and Te were deposited on cold substrates, rebuilding the crystal structure of V₂VI₃ compounds. Nanoalloyed super- lattices consisting of alternating Bi₂Te₃ and Sb₂Te₃ layers were grown with a thickness of 9 nm for the individual layers. The as-grown layers were annealed under different conditions to optimize the thermoelectric parameters. The obtained layers were investigated in their as-grown and annealed states using x-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive x-ray (EDX) spectroscopy, transmission electron microscopy (TEM), and electrical measurements. A lower limit of the elemental layer thickness was found to have c-orientation. Pure nanoalloyed Sb₂Te₃ layers were p-type as expected; however, it was impossible to synthesize p-type Bi₂Te₃ layers. Hence the Bi₂Te₃-Sb₂Te₃ superlattices consisting of alternating n- and p-type layers showed poor thermoelectric properties.     

Microstructures and Thermoelectric Properties of an Annealed Ti<Subscript>0.5</Subscript>(Hf<Subscript>0.5</Subscript>Zr<Subscript>0.5</Subscript>)<Subscript>0.5</Subscript>NiSn<Subscript>0.998</Subscript>Sb<Subscript>0.002</Subscript> Ribbon

The thermoelectric half-Heusler compound Ti_0.5(Hf_0.5Zr_0.5)_0.5NiSn_0.998Sb_0.002 was fabricated by spin-casting and subsequent annealing. ZT at room temperature increased with annealing time through an increase in absolute Seebeck coefficients despite a decrease in electrical conductivity. ZT reached 0.10 after annealing at 1050 K for 48 h. In powder x-ray diffraction analysis, each half-Heusler peak was accompanied by a bump at the high-angle side, corresponding to a minor Ti-rich half-Heusler phase. The quantity and Ti composition of the minor phase increased with annealing time, although those of the major half-Heusler phase were almost constant. In transmission electron microscopic analysis, granular domains, several nanometers in size, with atomic ordering or disordering were observed. Thermoelectric properties were␣improved by annealing through the growth of heterogeneous microstructures of the Ti-rich and Ti-poor half-Heusler grains and of the granular domains.     

Thermoelectric Properties of Spark Plasma-Sintered In<Subscript>4</Subscript>Se<Subscript>3</Subscript>-In<Subscript>4</Subscript>Te<Subscript>3</Subscript>

We report the thermoelectric properties of spark plasma-sintered In₄Se₃-In₄Te₃ materials. For comparison, pure In₄Se₃ and In₄Se₃ (80 wt.%)/In₄Te₃ (20 wt.%) mixture samples were prepared. In₄Se₃ and In₄Te₃ powders were synthesized by a conventional melting process in evacuated quartz ampoules, and a spark plasma method was used for the sintering of the pure In₄Se₃ and mixture samples. Thermoelectric and structural characterizations were carried out, and the mixing effect of In₄Se₃ and In₄Te₃ on the thermoelectric properties was investigated.     

Magnetic susceptibility of Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>-Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript> alloys

The magnetic susceptibility of Czochralski-grown single crystals of Bi₂Te₃-Sb₂Te₃ alloys containing 0, 10, 25, 40, 50, 60, 65, 70, 80, 90, 99.5, or 100 mol % Sb₂Te₃ has been investigated. The magnetic susceptibility of these crystals was determined at the temperature T = 291 K and the magnetic field H oriented parallel (χ_‖) and perpendicularly (χ_⊥) to the trigonal crystallographic axis C ₃. A complicated concentration dependence of the anisotropy of magnetic susceptibility χ_‖/χ_⊥ has been revealed. The crystals with the free carrier concentration p ≈ 5 × 10¹⁹ cm^?3 do not exhibit anisotropy of magnetic susceptibility. The transition to the isotropic magnetic state occurs for the compositions characterized by a significantly increased (from 200 to 300 meV) optical bandgap.     

Thermoelectric Properties of Zr<Subscript>3</Subscript>Mn<Subscript>4</Subscript>Si<Subscript>6</Subscript> and TiMnSi<Subscript>2</Subscript>

The Seebeck coefficient, electrical resistivity, and thermal conductivity of Zr₃Mn₄Si₆ and TiMnSi₂ were studied. The crystal lattices of these compounds contain relatively large open spaces, and, therefore, they have fairly low thermal conductivities (8.26 Wm⁻¹ K⁻¹ and 6.63 Wm⁻¹ K⁻¹, respectively) at room temperature. Their dimensionless figures of merit ZT were found to be 1.92 × 10⁻³ (at 1200 K) and 2.76 × 10⁻³ (at 900 K), respectively. The good electrical conductivities and low Seebeck coefficients might possibly be due to the fact that the distance between silicon atoms in these compounds is shorter than that in pure semiconductive silicon.     

Solid-State Reaction Mechanism and Deliquescence Phenomenon of K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>Nb<Subscript>0.7</Subscript>Al<Subscript>0.3</Subscript>O<Subscript>3</Subscript> Ceramic

Development of (K,Na)NbO₃-based ceramics has attracted much attention in recent decades. In this work, K_0.5Na_0.5Nb_0.7Al_0.3O₃ ceramic was prepared using conventional solid-state processing. A deliquescence phenomenon was observed when the specimen was exposed to moist atmosphere. The reaction mechanism and cause of deliquescence were investigated using x-ray diffraction analysis, scanning electron microscopy, energy-dispersive spectrometry, electron microprobe analysis, inductively coupled plasma mass spectrometry, and thermogravimetric/differential scanning calorimetric analysis. The results revealed interactions mainly amongst the raw materials K₂CO₃, Na₂CO₃, and Nb₂O₅ as well as K₂CO₃, Na₂CO₃, and Al₂O₃, which can influence the sintering behavior of the mixture. (K,Na)NbO₃ and (K,Na)AlO₂ were present in the sintered K_0.5Na_0.5Nb_0.7Al_0.3O₃ ceramic, with the latter leading to deliquescence. During the sintering process, Al₂O₃ reacts with alkali oxides (Na₂O and K₂O), which are the decomposition products of carbonates, to form (K,Na)AlO₂. In addition, Al₂O₃ is more likely to react with K₂O compared with Na₂O.     

Optical Study of Filled Tetrahedral Compounds Li<Subscript>3</Subscript>AlN<Subscript>2</Subscript> and Li<Subscript>3</Subscript>GaN<Subscript>2</Subscript>

A detailed analysis of the optical properties of filled tetrahedral semiconductors Li₃AlN₂ and Li₃GaN₂ has been performed, using the full potential linearized augmented plane wave method within the density functional theory. The real and imaginary parts of the dielectric function ε(ω), the optical absorption coefficient I(ω), the reflectivity R(ω), and the electron energy loss function are calculated within the random phase approximation. The interband transitions responsible for the structures in the spectra are specified. Looking at optical matrix element, we note that the major peaks are dominated by transition from metal s, N 2p states to N 2p, Ga 3d states. The theoretical calculated optical properties and electron energy loss spectrum yield a static dielectric constant of 5.34 and a plasmon energy of 19.47 eV for Li₃GaN₂. In the Li₃AlN₂ compound, the static dielectric constant decreases to 4.75 and yields a plasmon energy of 18.5 eV. The effect of spin–orbit coupling on the optical properties is also investigated and found to be quite small, especially in the low-energy region. In order to check the reliability of our calculations, analogous results obtained for Be₃N₂ in the same structure [space group Ia3(206)] are included in this work.     

Thermoelectric power of Bi<Subscript>92</Subscript>Sb<Subscript>8</Subscript> and Bi<Subscript>85</Subscript>Sb<Subscript>15</Subscript> thin films

The results of studying the galvanomagnetic and thermoelectric properties of thin block Bi₉₂Sb₈ and Bi₈₅Sb₁₅ films on mica and polyimide substrates are presented. The method used for measuring the thermoelectric power allowed us to study the temperature dependence the thermoelectric power, without introducing additional deformations into the substrate–film system. A significant difference in the temperature dependences of the galvanomagnetic and thermoelectric properties of films on mica and polyimide is found. The free charge-carrier concentrations and mobilities in the films on mica and polyimide and levels of the chemical potential for electrons and holes are calculated within the two-band approximation. The difference in the charge-carrier parameters for films on mica and polyimide is associated with strains in the film–substrate system.     

Characterization survey of Ga<Subscript>x</Subscript>In<Subscript>1−x</Subscript>As/InAs<Subscript>y</Subscript>P<Subscript>1−y</Subscript> double heterostructures and InAs<Subscript>y</Subscript>P<Subscript>1−y</Subscript> multilayers grown on InP

Low-bandgap, lattice-mismatched Ga_xIn_1−xAs (GaInAs) grown using InAs_yP_1−y (InAsP) compositional-step grades on InP is a primary choice for lightabsorbing, active layers in high-efficiency thermophotovoltaic (TPV) devices. The GaInAs/InAsP double heterostructures (DHs) show exceptional minority carrier lifetimes of up to several microseconds. We have performed a characterization survey of 0.4–0.6-eV GaInAs/InAsP DHs using a variety of techniques, including transmission electron microscopy (TEM). Dislocations are rarely observed to thread into the GaInAs active layers from the InAsP buffer layers that terminate the graded regions. Nearly complete strain relaxation occurs in buried regions of the InAsP grades. The buffer-layer strain prior to deposition of the active layer is virtually independent of the net misfit. Foreknowledge of this buffer-layer strain is essential to correctly lattice match the buffer to the GaInAs active layer.     

Nanotribological Characteristics of Cu<Subscript>6</Subscript>Sn<Subscript>5</Subscript>, Cu<Subscript>3</Subscript>Sn,and Ni<Subscript>3</Subscript>Sn<Subscript>4</Subscript> Intermetallic Compounds

Nanotribological characteristics, including the coefficient of friction, wear coefficient, and wear resistance, of Cu₆Sn₅, Cu₃Sn, and Ni₃Sn₄ intermetallic compounds developed by the annealing of Sn–Cu or Sn–Ni diffusion couples were investigated in this work. The scratch test conditions combined a constant normal load of 10 mN, 20 mN, or 30 mN and a scratch rate of 0.1 μm/s, 1 μm/s, or 10 μm/s. Experimental results indicated that, as the normal load increases, the pile-up grows taller and the scratch deepens, leading to a greater coefficient of friction and wear coefficient, and reduced wear resistance. Moreover, the scratch rate does not have a significant effect on the nanotribological characteristics except for those of Cu₆Sn₅ and Cu₃Sn under a normal load of 10 mN. Though the hardness of Cu₆Sn₅, Cu₃Sn, and Ni₃Sn₄ is similar, Ni₃Sn₄ appears to be more prone to wear damage.     

Thermal Stability of Barium and Indium Double-Filled Skutterudite Ba<Subscript>0.3</Subscript>In<Subscript>0.2</Subscript>Co<Subscript>3.95</Subscript>Ni<Subscript>0.05</Subscript>Sb<Subscript>12</Subscript> Coated by SiO<Subscript>2</Subscript> Nanoparticles

Filled skutterudite thermoelectric (TE) materials have been extensively studied to search for better TE materials in the past decade. However, there is no detailed investigation about the thermal stability of filled skutterudite TE materials. The evolution of microstructure and TE properties of nanostructured skutterudite materials fabricated with Ba_0.3In_0.2Co_3.95Ni_0.05Sb₁₂/SiO₂ core–shell composite particles with 3 nm thickness shell was investigated during periodic thermal cycling from room temperature to 723 K in this work. Scanning electronic microscopy and electron probe microscopy analysis were used to investigate the microstructure and chemical composition of the nanostructured skutterudite materials. TE properties of the nanostructured skutterudite materials were measured after every 200 cycles of quenching in the temperature range from 300 K to 800 K. The results show that the microstructure and composition of Ba_0.3In_0.2Co_3.95Ni_0.05Sb₁₂/SiO₂ nanostructured skutterudite materials were more stable than those of single-phase Ba_0.3In_0.2Co_3.95Ni_0.05Sb₁₂ bulk materials. The evolution of TE properties indicates that the electrical and thermal conductivity decrease along with an increase in the Seebeck coefficient with increasing quenching up to 2000 cycles. As a result, the dimensionless TE figure of merit (ZT) of the nanostructured skutterudite materials remains almost constant. It can be concluded that these nanostructured skutterudite materials have good thermal stability and are suitable for use in solar power generation systems.     

Characterization of Ge<Subscript>22</Subscript>Sb<Subscript>22</Subscript>Te<Subscript>56</Subscript> and Sb-Excess Ge<Subscript>15</Subscript>Sb<Subscript>47</Subscript>Te<Subscript>38</Subscript> Chalcogenide Thin Films for Phase-Change Memory Applications

A phase-change memory device that utilizes an antimony (Sb)-excess Ge₁₅Sb₄₇Te₃₈ chalcogenide thin film was fabricated and its electrical properties were measured and compared with a similar device that uses Ge₂₂Sb₂₂Te₅₆. The resulting electrical characteristics exhibited I _reset values of 14 mA for Ge₂₂Sb₂₂Te₅₆ and 10.6 mA for Ge₁₅Sb₄₇Te₃₈. Also, the set operation time (t _set) for the device using Ge₁₅Sb₄₇Te₃₈ films was 140 ns, which was more than twice as fast as the Ge₂₂Sb₂₂Te₅₆ device. The relationship between the microstructure and the improved electrical performance of the device was examined by means of transmission electron microscopy (TEM).     

Room-temperature photoluminescence of Ga<Subscript>0.96</Subscript>In<Subscript>0.04</Subscript>As<Subscript>0.11</Subscript>Sb<Subscript>0.89</Subscript> lattice matched to InAs

Photoluminescence (PL) has been observed at room temperature from a Ga_0.96In_0.04As_0.11Sb_0.89 quaternary solid solution for the first time. High-quality epitaxial layers of n-type (Te-doped) Ga_0.96In_0.04As_0.11Sb_0.89 with low In content were grown by liquid phase epitaxy (LPE) lattice-matched to InAs(100) substrates from a Ga-rich melt. The PL properties of the material were investigated over a wide temperature range, and the principal radiative transitions were identified. In the temperature range <150 K, donor-acceptor recombination involving the first and second ionization state of native antisite defects was the dominant radiative-recombination process, whereas interband recombination was found to dominate at room temperature.     

Structure and dielectric properties of Ba<Subscript>1−x</Subscript>Sr<Subscript>x</Subscript>ZnTi<Subscript>7</Subscript>O<Subscript>16</Subscript> hollandite ceramics

Hollandite-type Ba_1−xSr_xZnTi₇O₁₆ (x=0, 0.2, 0.4, 0.6, 0.8, and 1) ceramics have been synthesized by the conventional solid-state ceramic route. The phase purity and microstructure of these compositions have been characterized using x-ray diffraction (XRD) and scanning electron microscopy (SEM). The XRD analysis shows that an increase in strontium concentration in the A-site causes pairing of vacant tunnel sites, and hence the structure becomes unstable due to the collapse of the tunnel walls. The dielectric properties such as dielectric constant (ε_r), loss tangent (tan δ), and temperature variation of dielectric constant (τε_r) have been measured up to the 13 MHz region. The present study shows that zinc hollandites have relatively high dielectric constant and low loss tangent. The temperature variation of dielectric constant studies reveal that Ba-rich compositions have high positive τε_r and Sr-rich compositions have high negative τε_r in the 0–100°C region. Proper tailor making of these compositions has been attempted to arrive at near-zero temperature variation of the dielectric constant.     

Properties of CuIn<Subscript>3</Subscript>Se<Subscript>5</Subscript> crystals and In/CuIn<Subscript>3</Subscript>Se<Subscript>5</Subscript> structures

Using the method of planar crystallization from the melt with deviations from the stoichiometric composition, p-CuIn₃Se₅ single crystals are grown. The electrical properties of the homogeneous crystals are studied. It is found that the resistivity of the p-CuIn₃Se₅ crystals depends on the excess Se content in the melt. It is established that the voltaic photosensitivity of the In/CuIn₃Se₅ structures is enhanced with an increasing excess of Se content in the melt. The energy spectrum and the character of interband transitions in the CuIn₃Se₅ crystals are discussed. It is concluded that the CuIn₃Se₅ ternary compound can be used in high efficiency photoelectric converters of solar radiation.     

Ultra-Low Loss Microwave Dielectric Ceramic Li<Subscript>2</Subscript>Mg<Subscript>2</Subscript>TiO<Subscript>5</Subscript> and Low-Temperature Firing Via B<Subscript>2</Subscript>O<Subscript>3</Subscript> Addition

Li₂Mg₂TiO₅, a rock-salt structured ceramic fabricated by a solid-state sintering technique, was characterized at the microwave frequency band. As a result, a microwave dielectric permittivity (ε_r) of 13.4, a quality factor of 95,000 GHz (at 11.3 GHz), and a temperature coefficient of resonance frequency (τ_f) of ? 32.5 ppm/°C have been obtained at 1320°C. Li₂Mg₂TiO₅ ceramics have low permittivity, a broad processing temperature region, and a low loss, making them potential applications in millimeter-wave devices. Furthermore, B₂O₃ addition efficiently lowered the sintering temperature of Li₂Mg₂TiO₅ to 900°C, which opens up their possible applications in low-temperature co-fired ceramics (LTCC) technology.     

Optical Properties of K<Subscript>2</Subscript>O-Li<Subscript>2</Subscript>O-WO<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> Glasses: Evidence of Mixed Alkali Effect

Glass with compositions xK₂O-(30 ? x)Li₂O-10WO₃-60B₂O₃ for 0 ≤ x ≤ 30 mol.% have been prepared using the normal melt quenching technique. The optical reflection and absorption spectra were recorded at room temperature in the wavelength range 300–800 nm. From the absorption edge studies, the values of the optical band gap (E _opt) and Urbach energy (ΔE) have been evaluated. The values of E _opt and ΔE vary non-linearly with composition parameter, showing the mixed alkali effect. The dispersion of the refractive index is discussed in terms of the single oscillator Wemple Di-Domenico model.     

High-Temperature Capacitor Based on Ca-Doped Bi<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-BaTiO<Subscript>3</Subscript> Ceramics

High-temperature capacitors were prepared by the conventional oxide method based on Bi_0.5Na_0.5TiO₃-BaTiO₃-CaTiO₃ (BNT-BT-CT) lead-free piezoelectric ceramics. BNT-BT is one of the promising candidates as a high-temperature relaxor, and has a high Curie temperature and broadened dielectric constant. The addition of CT increases the dielectric constant at lower temperatures and decreases the dielectric constant at higher temperatures, so that the variation of capacitance is decreased. The effect of BT on the temperature characteristic of dielectric constant is contrary to that of CT. A single-phase rhombohedral perovskite and square grains were obtained in this study. With the proper amount of BT and CT additions, the high-temperature specification can be met: from −55°C to 200°C, the variation of capacitance is within ±15% of room-temperature capacitance.