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.     

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.     

Effect of Ca Doping on the Thermoelectric Performance of Yb<Subscript>14</Subscript>MnSb<Subscript>11</Subscript>

Complex Zintl phases possess low thermal conductivity and can be easily doped to modify the transport properties. Therefore, these phases have the potential to be good thermoelectric materials by simply controlling carrier concentration. Yb₁₄MnSb₁₁ is a Zintl phase that has shown promise as a p-type thermoelectric material for high-temperature power generation. A Sn-flux synthetic route was used to make the new phase, Yb₁₃CaMnSb₁₁. The high-temperature thermoelectric properties were measured on polycrystalline hot-pressed pellets and compared with Yb₁₄MnSb₁₁. Substitution of the lighter isovalent Ca for Yb should reduce the lattice thermal conductivity by mass disorder scattering, and a noticeable reduction is seen in thermal diffusivity measurements at high temperature. There may also be a carrier concentration effect by employing the more electropositive Ca.     

Structural Phase Transitions and Thermoelectric Properties of AgPb<Subscript>18</Subscript>SbTe<Subscript>20</Subscript> Under Compression

The high-figure-of-merit thermoelectric material AgPb₁₈SbTe₂₀ has been investigated by in situ angular-dispersive x-ray diffraction (XRD) and x-ray absorption fine-structure (XAFS) measurements up to 30 GPa. Resistivity and thermopower were measured with Bridgman-type opposed metal anvil cells. The results show that the ambient cubic ( Fm[`3] m ) \left( {Fm\overline{3} m} \right) structure transforms to orthorhombic (Pnma) at 6.4 GPa and then to the CsCl-type ( Pm[`3] m ) \left( {Pm\overline{3} m} \right) structure at 15 GPa. The ambient cubic ( Fm[`3] m ) \left( {Fm\overline{3} m} \right) phase is found to be recoverable on releasing the pressure. The thermoelectric power is found to increase with pressure for the cubic phase. The XAFS studies performed at the Pb L ₃-edge and Ag K-edge along with resistivity studies complement the XRD findings.     

Conduction Mechanisms in Multiferroic Multilayer BaTiO<Subscript>3</Subscript>/NiFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/BaTiO<Subscript>3</Subscript> Memristors

Memristive devices and materials are extensively studied as they offer diverse properties and applications in digital, analog and bio-inspired circuits. In this paper, we present an important class of memristors, multiferroic memristors, which are composed of multiferroic multilayer BaTiO₃/NiFe₂O₄/BaTiO₃ thin films, fabricated by a spin-coating deposition technique on platinized Si wafers. This cost-effective device shows symmetric and reproducible current–voltage characteristics for the actuating voltage amplitude of ±10 V. The origin of the conduction mechanism was investigated by measuring the electrical response in different voltage and temperature conditions. The results indicate the existence of two mechanisms: thermionic emission and Fowler–Nordheim tunnelling, which alternate with actuating voltage amplitude and operating temperature.     

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.     

Low-Temperature Thermoelectric Properties of Co<Subscript>0.9</Subscript>Fe<Subscript>0.1</Subscript>Sb<Subscript>3</Subscript>-Based Skutterudite Nanocomposites with FeSb<Subscript>2</Subscript> Nanoinclusions

Bulk thermoelectric nanocomposite materials have great potential to exhibit higher ZT due to effects arising from their nanostructure. Herein, we report low-temperature thermoelectric properties of Co_0.9Fe_0.1Sb₃-based skutterudite nanocomposites containing FeSb₂ nanoinclusions. These nanocomposites can be easily synthesized by melting and rapid water quenching. The nanoscale FeSb₂ precipitates are well dispersed in the skutterudite matrix and reduce the lattice thermal conductivity due to additional phonon scattering from nanoscopic interfaces. Moreover, the nanocomposite samples also exhibit enhanced Seebeck coefficients relative to regular iron-substituted skutterudite samples. As a result, our best nanocomposite sample boasts a ZT = 0.041 at 300 K, which is nearly three times as large as that for Co_0.9Fe_0.1Sb₃ previously reported.     

Electronic structure of single-layer superlattices (GeC)<Subscript>1</Subscript>(SiC)<Subscript>1</Subscript>, (SnC)<Subscript>1</Subscript>(SiC)<Subscript>1</Subscript>, and (SnC)<Subscript>1</Subscript>(GeC)<Subscript>1</Subscript>

The crystal and electronic structures of GeC, SiC, and SnC crystals and superlattices based on them, GeC/SiC, SnC/SiC, and SnC/GeC, are modeled within density functional theory. The equilibrium lattice constants are obtained, the band spectra and densities of states are calculated, and the specific features of the formation of the valence band and chemical bonding in these crystals and superlattices are studied.     

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.     

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.     

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.     

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.     

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.     

Crystallization behavior and ferroelectric properties of PbTiO<Subscript>3</Subscript>/Ba<Subscript>0.85</Subscript>Sr<Subscript>0.15</Subscript>TiO<Subscript>3</Subscript>/PbTiO<Subscript>3</Subscript> sandwich thin film on Pt/Ti/SiO<Subscript>2</Subscript>/Si substrates

A PbTiO₃/Ba_0.85Sr_0.15TiO₃/PbTiO₃ (PT/BST15/PT) sandwich thin film has been prepared on Pt/Ti/SiO₂/Si substrates by an improved sol-gel technique. It is found that such films under rapid thermal annealing at 700°C crystallize more favorably with the addition of a PbTiO₃ layer. They possess a pure, perovskite-phase structure with a random orientation. The polarization-electric field (P-E) hysteresis loop and current-voltage (I-V) characteristic curves reveal that a PT/BST15/PT film exhibits good ferroelectricity at room temperature. However, no sharp peak, only a weak maximum, is observed in the curves of the dielectric constant versus temperature. The dielectric constant, loss tangent, leakage current density at 20 kV/cm, remnant polarization, and coercive field of the PT/BST15/PT film are 438, 0.025, 1.3 × 10⁻⁶ Acm⁻², 2.46 μCcm⁻², and 41 kVcm⁻¹, respectively, at 25°C and 10 kHz. The PT/BST15/PT film is a candidate material for high sensitivity elements for uncooled, infrared, focal plane arrays (UFPAs) to be used at near ambient temperature.     

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.     

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).     

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.     

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.