Effect of Vacancy Distribution on the Thermal Conductivity of Ga<Subscript>2</Subscript>Te<Subscript>3</Subscript> and Ga<Subscript>2</Subscript>Se<Subscript>3</Subscript>

Our group has focused attention on Ga₂Te₃ as a natural nanostructured thermoelectric material. Ga₂Te₃ has basically a zincblende structure, but one-third of the Ga sites are structural vacancies due to the valence mismatch between Ga and Te. It has been confirmed that (1) vacancies in Ga₂Te₃ exist as two-dimensional (2D) vacancy planes, and (2) Ga₂Te₃ exhibits an unexpectedly low thermal conductivity (κ), most likely due to highly effective phonon scattering by the 2D vacancy planes. However, the effect of the size and periodicity of the 2D vacancy planes on κ has been unclear. In addition, it has also been unclear whether only the 2D vacancy planes reduce κ or if point-type vacancies can also reduce κ. In the present study, we tried to prepare Ga₂Te₃ and Ga₂Se₃ with various vacancy distributions by controlling annealing conditions. The atomic structures of the samples were characterized by means of transmission electron microscopy, and κ was evaluated from the thermal diffusivity measured by the laser flash method. The effects of vacancy distributions on κ of Ga₂Te₃ and Ga₂Se₃ are discussed.     

Effects of Pulsed Laser Deposition Conditions on the Microstructure of Ca<Subscript>3</Subscript>Co<Subscript>4</Subscript>O<Subscript>9</Subscript> Thin Films

The influence of deposition conditions on the microstructure of Ca₃Co₄O₉ (CCO) thin films fabricated by the pulsed laser deposition technique was investigated. X-ray diffraction revealed that a fast deposition rate resulted in not only low crystallinity but also the existence of the Ca _x CoO₂ secondary phase. The Ca _x CoO₂ structure was further confirmed by high-resolution transmission electron microscopy. The CCO thin-film growth was deduced to be a kinetically controlled process, and the quality of the thin films strongly depended on the coalescence process. The formation of Ca _x CoO₂ was inevitable during the thin-film growth. However, given enough time and supply of oxygen at a lower deposition rate, it was possible to transform the Ca _x CoO₂ phase into the desired CCO phase during the coalescence process, while with faster deposition, more Ca _x CoO₂ structure was formed, and the secondary phase could hardly transform into the CCO phase.     

Thermoelectric Properties of Na<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>CoO<Subscript>2</Subscript> and Prospects for Other Oxide Thermoelectrics

We discuss the thermoelectric properties of Na _x CoO₂ using the electronic structure, as determined in first principles calculations, and Boltzmann kinetic transport theory. The Fermi energy lies near the top of a manifold of Co t _2g bands. These t _2g bands are separated by a large gap from the higher-lying e _g states. Although the large crystal-field splitting implies substantial Co–O hybridization, the bands are narrow. Application of standard Boltzmann transport theory to such a narrow band structure yields high thermopowers in accord with experimental observations, even for high metallic carrier densities. The high thermopowers observed for Na _x CoO₂ can therefore be explained by standard band theory and do not rely on low dimensionality or correlation effects specific to Co. We also present results for the cubic spinel structure ZnRh₂O₄. Like Na _x CoO₂, this compound has very narrow valence bands. We find that if it could be doped with mobile carriers, it would also have a high thermopower, comparable with that of Na _x CoO₂.     

Discommensuration of Doped [Ca<Subscript>2</Subscript>CoO<Subscript>3</Subscript>]<Subscript><Emphasis Type="Italic">p</Emphasis></Subscript>CoO<Subscript>2</Subscript>

Single-crystal x-ray diffraction and high-resolution electron microscopy studies were carried out for Co-121 ([Ca₂CoO₃] _p CoO₂) and Sr-doped Co-121 grown in a KCl flux at 810°C. Typically, the samples were 2 mm × 2 mm × 0.02 mm in size. The single-crystal diffraction intensities were measured by the use of a four-circle diffractometer. Twinned super reflections, e.g., and were observed in the electron diffraction patterns. These super reflections were not observed in the end-member. Diffuse scattering was observed in the same reciprocal space by the single-crystal x-ray diffraction study. A discommensurate crystal model is proposed for the Sr-doped system.     

Thermoelectric Properties of the One-Dimensional Cobalt Oxide CaCo<Subscript>2</Subscript>O<Subscript>4</Subscript>

In this work we studied the crystal structure and physical properties of the new one-dimensional cobalt oxide CaCo₂O_4+δ . The CaCo₂O_4+δ phase crystallizes as a calcium-ferrite-type structure, which consists of a corner- and edge-shared CoO₆ octahedron network including one-dimensional double chains. The specific-heat Sommerfeld constant γ was found to be 4.48(7) mJ/mol K². This result suggests that the CaCo₂O_4+δ phase has a finite density of states at the Fermi level. Metallic temperature dependence of the Seebeck coefficient S with a large thermoelectric power (S = 151 μV/K at 387 K) was observed. The origin of the large thermoelectric power may be attributed to the quasi one-dimensional character of the energy band near the valence band maximum in CaCo₂O_4+δ .     

Electronic states on silicon surface after deposition and annealing of SiO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> films

The spectrum of the photoconductivity induced by the polarization field of charges at surface states and traps in the film bulk has been analyzed to determine the energy band diagram at the c-Si-SiO _x interface and the changes in the electronic states after the film annealing. It is found that the energy bands are bent at the Si-SiO _x interface and the Si surface is enriched in electrons. In equilibrium the photocurrent peak at 1.1 eV is due to the band-to-band transitions in the silicon part of the interface. Annealing shifts the peak to higher energies; this shift increases with an increase in the annealing temperature from 650 to 1000°C. This effect is accompanied by a decrease in the photocurrent at ≤1.1 eV and weakening of the band-edge photoluminescence near the Si surface. The changes revealed are explained by the formation of an oxide layer with Si nanoclusters at the Si-SiO _x interface upon annealing. This process is caused by oxygen diffusion from the SiO _x film, which occurs mainly via defects on the Si wafer surface. The photoconductivity spectrum of the samples charged by short-term application of a negative potential to silicon exhibits electronic transitions in the SiO _x film, both from the matrix electronic states and from the states of the defects and Si nanoclusters in the film.     

Effect of Ionic Radius and Resultant Two-Dimensionality of Phonons on Thermal Conductivity in M<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>CoO<Subscript>2</Subscript> (M = Li,Na, K) by Perturbed Molecular Dynamics

Phonon thermal conductivity calculations for Li _x CoO₂, Na _x CoO₂, and K _x CoO₂ (x = 1, 0.5) have been carried out by perturbed molecular dynamics to clarify the dependence of thermal conductivity on alkali-metal vacancy concentration in these materials. While thermal conductivity decreased for all compounds upon introduction of alkali-metal vacancies, the magnitude of the decrease is strongly dependent on the size of the alkali-metal ion. Further numerical analyses using fictitious physical parameters reveal that, with increasing ionic radius, the two-dimensionality of the phonons in the CoO₂ layers, which are responsible for overall thermal conductivity, is enhanced, resulting in lower thermal conductivity in vacancy-free compounds as well as ineffectiveness of alkali-metal vacancies in lowering thermal conductivity. In contrast, for systems with smaller alkali-metal ionic radius, even though higher thermal conductivity is predicted when no vacancies are present, vacancies are quite effective in significantly lowering thermal conductivity by modifying phonon states in the CoO₂ layers, more so than in systems with larger alkali-metal vacancies.     

Thermoelectric Properties of Mn-Doped Ca<Subscript>5</Subscript>Al<Subscript>2</Subscript>Sb<Subscript>6</Subscript>

Ca₅Al₂Sb₆ is a relatively inexpensive Zintl compound exhibiting promising thermoelectric efficiency at temperatures suitable for waste heat recovery. Motivated by our previous studies of Ca₅Al₂Sb₆ doped with Na and Zn, this study focuses on doping with Mn²⁺ at the Al³⁺ site. While Mn is a successful p-type dopant in Ca₅Al₂Sb₆, we find that incomplete dopant activation yields lower hole concentrations than obtained with either previously investigated dopant. High-temperature Hall effect and Seebeck coefficient measurements show a transition from nondegenerate to degenerate semiconducting behavior in Ca₅Al_2−x Mn _x Sb₆ samples (x = 0.05, 0.1, 0.2, 0.3, 0.4) with increasing Mn content. Ultimately, no improvement in zT is achieved via Mn doping, due in part to the limited carrier concentration range achieved.     

Dielectric Properties of (Bi<Subscript>0.5</Subscript>K<Subscript>0.5</Subscript>)ZrO<Subscript>3</Subscript> Modified (K<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>)NbO<Subscript>3</Subscript> Ceramics as High-Temperature Ceramic Capacitors

(1???x)K_0.5Na_0.5NbO₃-x(Bi_0.5K_0.5)ZrO₃ [abbreviated as (1???x)KNN-xBKZ, 0?≤?x?≤?0.08] lead-free ceramics have been fabricated by a solid-state processing route. Based on the x-ray diffraction data and temperature-dependent dielectric characteristics, an orthorhombic phase for x?≤?0.03 and single rhombohedral one for x?≥?0.05 at room temperature were determined. The cell volume firstly increases, then decreases and finally increases with increasing BKZ, depending on ionic size and crystallographic structure. For the sample of x?=?0.05, a temperature-stable high permittivity (~?1736?±?15%) along with low dielectric loss tangent (≤?5%) is recorded from 158°C to 407°C. In addition, the activation energies of dielectric relaxation and dc conductivity at high temperatures were characterized by impedance spectroscopy. A combined effect of lattice distortion and oxygen vacancies on the magnitude of activation energies was discussed.     

Al ohmic contacts to HCI-treated Mg<Subscript>x</Subscript>Zn<Subscript>1−x</Subscript>O

The Al nonalloyed ohmic contacts were fabricated on Mg_xZn_1−xO (0≤x≤0.2) thin films. HCl surface treatment significantly reduced the specific contact resistances to value around 10⁻⁴ Ω cm². X-ray photoelectron spectroscopy (XPS) analysis revealed that the HCl treatment increased the oxygen vacancy density and introduced chlorine to the semiconductor surface, resulting in a thin conductive layer and thus reduced specific contact resistance. A subsequent oxygen plasma treatment reduced the oxygen vacancy density, and correspondingly increased the specific contact resistance. Al-ZnO contacts were insensitive to the HCl treatment, due to the formation of a highly conductive Al-doped thin interface layer.     

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.     

Optical and dielectric characteristics of the rare-earth metal oxide Lu<Subscript>2</Subscript>O<Subscript>3</Subscript>

The characteristics of the Lu₂O₃ oxide and their variations controlled by compositional defects are studied. The defects are anion vacancies produced on partial reduction of the oxide. Such defects exhibit features typical of quantum objects and have a profound effect on the optical transmittance spectrum, the character of conduction (insulator or semiconductor properties) and the order of magnitude of the permittivity ɛ (capable of varying from 11.2 to 125). The structural features of vacancies in the oxides are considered, and the effect of vacancies on the polarization, conductivity, and lattice vibrations is studied. The studies are carried out in the temperature range 200–900 K, the wavelength range 0.03–50 μm, and the current frequency range 10²–10⁵ Hz. The rare-earth metal oxides attract interest for applications in microelectronics due to their high permittivity (several times higher than the permittivity of SiO₂) and, hence, the prospects for use of these oxides instead of SiO₂.     

Electrical and Thermal Conductivity and Conduction Mechanism of Ge<Subscript>2</Subscript>Sb<Subscript>2</Subscript>Te<Subscript>5</Subscript> Alloy

Ge₂Sb₂Te₅ alloy has drawn much attention due to its application in phase-change random-access memory and potential as a thermoelectric material. Electrical and thermal conductivity are important material properties in both applications. The aim of this work is to investigate the temperature dependence of the electrical and thermal conductivity of Ge₂Sb₂Te₅ alloy and discuss the thermal conduction mechanism. The electrical resistivity and thermal conductivity of Ge₂Sb₂Te₅ alloy were measured from room temperature to 823 K by four-terminal and hot-strip method, respectively. With increasing temperature, the electrical resistivity increased while the thermal conductivity first decreased up to about 600 K then increased. The electronic component of the thermal conductivity was calculated from the Wiedemann–Franz law using the resistivity results. At room temperature, Ge₂Sb₂Te₅ alloy has large electronic thermal conductivity and low lattice thermal conductivity. Bipolar diffusion contributes more to the thermal conductivity with increasing temperature. The special crystallographic structure of Ge₂Sb₂Te₅ alloy accounts for the thermal conduction mechanism.     

The effect of irradiation with electrons on the electrical parameters of Hg<Subscript>3</Subscript>In<Subscript>2</Subscript>Te<Subscript>6</Subscript>

The results of studying the electrical properties of Hg₃In₂Te₆ crystals irradiated with electrons with the energy E _e = 18 MeV and the dose D = 4 × 10¹⁶ cm⁻² are reported. It is shown that, irrespective of the charge-carrier concentration in the initial material, the Hg₃In₂Te₆ samples acquire the charge-carrier concentration (1.6–1.8) × 10¹³ cm⁻³ after irradiation. The phenomenon of Fermi level pinning in an irradiated material is discussed. The initial charge-carrier concentration, which remains virtually unchanged after irradiation and which ensures the high radiation resistance of Hg₃In₂Te₆ crystals, corresponds to a compensated material, similar to an intrinsic semiconductor at T > 260 K.     

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.     

Impression Creep of a Lead-Free Sn-1.7Sb-1.5Ag Solder Reinforced by Submicron-Size Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Particles

In the present study, the Sn-1.7Sb-1.5Ag solder alloy and the same material reinforced with 5 vol.% of 0.3-μm Al₂O₃ particles were synthesized using the powder metallurgy route of blending, compaction, sintering, and extrusion. The impression creep behavior of both monolithic and composite solders was studied under a constant punching stress in the range of 20 MPa to 110 MPa, at temperatures in the range of 320 K to 430 K. The creep resistance of the composite solder was higher than that of the monolithic alloy at all applied stresses and temperatures, as indicated by their corresponding minimum creep rates. This was attributed to the dispersive distribution of the submicron-sized Al₂O₃ particles in the composite solder. Assuming a power-law relationship between the impression stress and velocity, average stress exponents of 5.3 to 5.6 and 5.8 to 5.9 were obtained for the monolithic and composite materials, respectively. Analysis of the data showed that, for all loads and temperatures, the activation energy for both materials was almost stress independent, with average values of 44.0 kJ mol⁻¹ and 41.6 kJ mol⁻¹ for the monolithic and composite solders, respectively. These activation energies are close to the value of 46 kJ mol⁻¹ for dislocation climb, assisted by vacancy diffusion through dislocation cores in the Sn. This, together with the stress exponents of about 5 to 5.9, suggests that the operative creep mechanism is dislocation viscous glide controlled by dislocation pipe diffusion.     

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.     

Charge transport in thin layers of ferroelectric Hf<Subscript>0.5</Subscript>Zr<Subscript>0.5</Subscript>O<Subscript>2</Subscript>

The mechanism responsible for the charge transport in thin ferroelectric Hf_0.5Zr_0.5O₂ films has been studied. It is shown that in these films the transport mechanism is phonon-assisted tunneling between the traps. The optimal thickness of dielectric film for TiN/Hf_0.5Zr_0.5O₂/Pt structures is determined. As a result of comparing the experimental current–voltage (I–V) characteristics of TiN/Hf_0.5Zr_0.5O₂/Pt structures with the calculated ones, the thermal and optical energies of the traps are determined and the concentration of the traps is estimated. A comparison between the transport properties of ferroelectric and amorphous Hf_0.5Zr_0.5O₂ films is carried out. It is shown that the charge transport mechanism in this dielectric does not depend on its crystalline phase. A method for decreasing leakage currents in Hf_0.5Zr_0.5O₂ is proposed. A study of the resource of repolarization cycles for TiN/Hf_0.5Zr_0.5O₂/TiN metal-dielectric-metal (MDM) structures fully grown by atomic layer deposition (ALD) has been carried out.     

Effects of Cooling Rate on Thermoelectric Properties of <Emphasis Type="Italic">n</Emphasis>-Type Bi<Subscript>2</Subscript>(Se<Subscript>0.4</Subscript>Te<Subscript>0.6</Subscript>)<Subscript>3</Subscript> Compounds

A series of Bi₂(Se_0.4Te_0.6)₃ compounds were synthesized by a rapid route of melt spinning (MS) combined with a subsequent spark plasma sintering (SPS) process. Measurements of the Seebeck coefficient, electrical conductivity, and thermal conductivity were performed over the temperature range from 300 K to 520 K. The measurement results showed that the cooling rate of melt spinning had a significant impact on the transport properties of electrons and phonons, effectively enhancing the thermoelectric properties of the compounds. The maximum ZT value reached 0.93 at 460 K for the sample prepared with the highest cooling rate, and infrared spectrum measurement results showed that the compound with lower tellurium content, Bi₂(Se_0.4Te_0.6)₃, possesses a larger optical forbidden gap (E _g) compared with the traditional n-type zone-melted material with formula Bi₂(Se_0.07Te_0.93)₃. Our work provides a new approach to develop low-tellurium-bearing Bi₂Te₃-based compounds with good thermoelectric performance.