Thermoelectric Properties of Cu-doped Bi<Subscript>0.4</Subscript>Sb<Subscript>1.6</Subscript>Te<Subscript>3</Subscript> Prepared by Hot Extrusion

Cu_0.003Bi_0.4Sb_1.6Te₃ alloys were prepared by using encapsulated melting and hot extrusion (HE). The hot-extruded specimens had the relative average density of 98%. The (00l) planes were preferentially oriented parallel to the extrusion direction, but the specimens showed low crystallographic anisotropy with low orientation factors. The specimens were hot-extruded at 698 K, and they showed excellent mechanical properties with a Vickers hardness of 76 Hv and a bending strength of 59 MPa. However, as the HE temperature increased, the mechanical properties degraded due to grain growth. The hot-extruded specimens showed positive Seebeck coefficients, indicating that the specimens have p-type conduction. These specimens exhibited negative temperature dependences of electrical conductivity, and thus behaved as degenerate semiconductors. The Seebeck coefficient reached the maximum value at 373 K and then decreased with increasing temperature due to intrinsic conduction. Cu-doped specimens exhibited high power factors due to relatively higher electrical conductivities and Seebeck coefficients than those of undoped specimens. A thermal conductivity of 1.00 Wm^?1 K^?1 was obtained at 373 K for Cu_0.003Bi_0.4Sb_1.6Te₃ hot-extruded at 723 K. A maximum dimensionless figure of merit, ZT _max = 1.05, and an average dimensionless figure of merit, ZT _ave = 0.98, were achieved at 373 K.     

Specific thermoelectric properties of lightly doped Bi<Subscript>2</Subscript>(TeSe)<Subscript>3</Subscript> solid solutions

Electrical and thermoelectric properties of a lightly doped n-Bi₂Te_2.7Se_0.3 solid solution have been studied in the temperature range 77–300 K. The results are compared with data for the compound PbTe_0.9Se_0.1 with a similar magnitude of the Seebeck coefficient S at 84 K. Along with lower thermal conductivity, Bi₂Te_2.7Se_0.3 has a higher electrical conductivity σ and a much weaker temperature dependence. As a result, the power coefficient S ²σ in optimal samples begins to decrease only when the density of minority carriers becomes significant. In this case, |S| considerably exceeds the standard value of 200 μV/K. The reduction of the electron density reduces the thermoelectric figure of merit Z at its maximum and slightly lowers the temperature of the maximum; therefore, the expected effect on the average value of Z in the range 77–300 K is absent. Similar behavior is observed in Bi₂Te_2.88Se_0.12, although the effect is less pronounced. The experimental results are discussed taking into account possible changes in the dominant scattering mechanisms, carrier density, and electron energy spectrum. __________ Translated from Fizika i Tekhnika Poluprovodnikov, Vol. 38, No. 7, 2004, pp. 811–815. Original Russian Text Copyright ? 2004 by Konstantinov, Prokof’eva, Ravich, Fedorov, Kompaniets.     

Effect of thallium doping on the mobility of electrons in Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript> and holes in Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript>

The Shubnikov–de Haas effect and the Hall effect in n-Bi_2–xTl_xSe₃ (x = 0, 0.01, 0.02, 0.04) and p-Sb_2–xTl_xTe₃ (x = 0, 0.005, 0.015, 0.05) single crystals are studied. The carrier mobilities and their changes upon Tl doping are calculated by the Fourier spectra of oscillations. It is found shown that Tl doping decreases the electron concentration in n-Bi_2–xTl_xSe₃ and increases the electron mobility. In p-Sb_2–xTl_xTe₃, both the hole concentration and mobility decrease upon Tl doping. The change in the crystal defect concentration, which leads to these effects, is discussed.     

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.     

Effect of ZnO Nanoparticles on the Sintering Behavior and Physical Properties of Bi<Subscript>0.5</Subscript>(Na<Subscript>0.8</Subscript>K<Subscript>0.2</Subscript>)<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> Lead-Free Ceramics

Sintered Bi_0.5(Na_0.8K_0.2)_0.5TiO₃ + x wt.% ZnO nanoparticle (BNKT–xZnO_n) ceramics have been fabricated by conventional annealing with the aid of ultrasound waves for preliminary milling. Because of the presence of the liquid Bi₂O₃–ZnO phase at the eutectic point of 738°C, the sintering temperature decreased from 1150°C to 1000°C, and the morphology phase boundary of BNKT–xZnO_n ceramics can be clarified by two separated peaks at (002)_T and (200)_T of 2θ in the x-ray diffraction (XRD) patterns. The improvement of ferroelectric properties has been obtained for BNZT–0.2 wt.% ZnO_n ceramics by the increase of remanent polarization up to 20.4 μC/cm² and a decrease of electric coercive field down to 14.2 kV/cm. The piezoelectric parameters of the ceramic included a piezoelectric charge constant of d ₃₁ = 78 pC/N; electromechanical coupling factors k _p = 0.31 and k _t = 0.34, larger than the values of 42 pC/N, 0.12 and 0.13, respectively, were obtained for the BNKT ceramics.     

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.     

Effect of copper doping on kinetic phenomena in <Emphasis Type="Italic">n</Emphasis>-Bi<Subscript>2</Subscript>Te<Subscript>2.85</Subscript>Se<Subscript>0.15</Subscript>

In single crystals of copper-doped and undoped Bi₂Te_2.85Se_0.15 solid solutions with an electron concentration close to 1 × 10¹⁹ cm^?3, the temperature dependences are investigated for the Hall (R ₁₂₃, R ₃₂₁) and Seebeck (S ₁₁) kinetic coefficients, the electrical-conductivity (σ ₁₁), Nernst-Ettingshausen (Q ₁₂₃), and thermalconductivity (k ₁₁) coefficients in the temperature range of 77–400 K. The absence of noticeable anomalies in the temperature dependences of the kinetic coefficients makes it possible to use the one-band model when analyzing the experimental results. Within the framework of the one-band model, the effective mass of density of states (m _d ≈ 0.8m ₀), the energy gap (ε_g ≈ 0.2 eV), and the effective scattering parameter (r _eff ≈ 0.2) are estimated. The obtained value of the parameter r _eff is indicative of the mixed electron-scattering mechanism with the dominant scattering by acoustic phonons. Data on the thermal conductivity and the lattice resistivity obtained by subtracting the electron contribution according to the Wiedemann-Franz law are presented.     

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 for a Suspended Microribbon of Quasi-One-Dimensional TiS<Subscript>3</Subscript>

Transition-metal trichalcogenides MX₃ (M = Ti, Zr, Nb, Ta; X = S, Se) are well-known inorganic quasi-one-dimensional conductors. Among them, we have investigated the thermoelectric properties of titanium trisulfide TiS₃ microribbon. The electrical resistivity ρ, thermal conductivity κ, and thermoelectric power S were measured using 3ω method. The weight mean values were found to be ρ = 5 mω m and κ = 10 W K^?1 m^?1 along the one-dimensional direction (b-axis) of the TiS₃ microribbon. Combined with the thermoelectric power S = ?530 μV K^?1, the figure of merit was calculated as ZT = 0.0023. This efficiency is the same as that of randomly oriented bulk TiS₃. We also estimated the anisotropy of σ and κ using the present results and those for randomly oriented bulk material. The obtained weak anisotropy for TiS₃ is attributable to strong coupling between triangular columns consisting of TiS₃ units. These experimental results are consistent with theoretical results obtained using density functional theory (DFT) calculations.     

Effects of Nb Content on the Ferroelectric and Dielectric Properties of Nb/Nd-Co-doped Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> Thin Films

Nd/Nb-co-substituted Bi_3.15Nd_0.85Ti_3?x Nb _x O₁₂ (BNTN _x , x = 0.01, 0.03, 0.05 and 0.07) thin films were grown on Pt/Ti/SiO₂/Si (100) substrates by chemical solution deposition. The effects of Nb content on the micro-structural, dielectric, ferroelectric, leakage current and capacitive properties of the BNTN _x thin films were investigated. A low-concentration substitution with Nb ions in BNTN _x can greatly enhance its remanent polarization (2P _r) and reduce the coercive field (2E _c) compared with those of Bi₄Ti₃O₁₂ (BIT) thin film. The highest 2P _r (71.4 μC/cm²) was observed in the BNTN_0.03 thin film when the 2E _c was 202 kV/cm. Leakage currents of all the films were on the order of 10^?6 to 10^?5 A/cm², and the BNTN_0.03 thin film has a minimum leakage current (2.1 × 10^?6 A/cm²) under the high electric field (267 kV/cm). Besides, the C–V curve of the BNTN_0.03 thin film is the most symmetrical, and the maximum tunability (21.0%) was also observed in this film. The BNTN_0.03 thin film shows the largest dielectric constant and the lowest dielectric loss and its maximum Curie temperature is 410 ± 5°C.     

Theoretical Study of Electronic Structure and Thermoelectric Properties of Doped CuAlO<Subscript>2</Subscript>

The doping level dependence of thermoelectric properties of delafossite CuAlO₂ has been investigated in the constant scattering time (τ) approximation, starting from the first principles of electronic structure. In particular, the lattice parameters and the energy band structure were calculated using the total energy plane-wave pseudopotential method. It was found that the lattice parameters of CuAlO₂ are a = 2.802 Å and c = 16.704 Å, and the internal parameter is u = 0.1097. CuAlO₂ has an indirect band gap of 2.17 eV and a direct gap of 3.31 eV. The calculated energy band structures were then used to calculate the electrical transport coefficients of CuAlO₂. By considering the effects of doping level and temperature, it was found that the Seebeck coefficient S(T) increases with increasing acceptor doping (A _d) level. The values of S(T) in our experiments correspond to an A _d level at 0.262 eV, which is identified as the Fermi level of CuAlO₂. Based on our experimental Seebeck coefficient and the electrical conductivity, the constant relaxation time is estimated to be 1 × 10^?16 s. The power factor is large for a low A _d level and increases with temperature. It is suggested that delafossite CuAlO₂ can be considered as a promising thermoelectric oxide material at high doping and high temperature.     

Electronic Processes in CdIn<Subscript>2</Subscript>Te<Subscript>4</Subscript> Crystals

The results of investigations of electrical, optical, and photoelectric properties of CdIn₂Te⁴ crystals, which were grown by the Bridgman method are presented. It is shown that electrical conductivity is determined mainly by electrons with the effective mass m_n = 0.44m₀ and the mobility 120–140 cm²/(V s), which weakly depends on temperature. CdIn₂Te₄ behaves as a partially compensated semiconductor with the donor-center ionization energy E_d = 0.38 eV and the compensation level K = N_a/N_d = 0.36. The absorption-coefficient spectra at the energy hν < E_g = 1.27 eV are subject to the Urbach rule with a typical energy of 18–25 meV. The photoconductivity depends on the sample thickness. The diffusion length, the charge-carrier lifetime, and the surface-recombination rate are determined from the photoconductivity spectra.     

Crystalline SiN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Ultrathin Films Grown on AlGaN/GaN Using <Emphasis Type="Italic">In Situ</Emphasis> Metalorganic Chemical Vapor Deposition

Surface passivation by SiN _x films is indispensable for high-power operation of AlGaN/GaN heterojunction field-effect transistors (HFETs) since it can effectively suppress collapse in the drain current. So far, the plasma-enhanced chemical vapor deposition technique has been used for the SiN _x deposition; however, possible damage induced by the plasma processing may affect direct-current performance or reliability. In this paper, we present subsequent deposition of SiN _x ultrathin films on AlGaN/GaN in the same metalorganic chemical vapor deposition reactor. It is experimentally found that this in situ SiN _x passivation doubles the sheet carrier density at the AlGaN/GaN interface from that of the unpassivated sample. High-resolution cross-sectional transmission electron microscopy reveals that in situ SiN _x is crystallized on the AlGaN layer as island-like structures via the Stranski-Krastanov growth mode. The lattice constants of in situ SiN _x are estimated to be a ≈ 3.2 Å and c ≈ 2.4 Å, which are quite different from those of well-known Si₃N₄ crystal structures. First-principles calculation predicts that the crystal structure of in situ SiN _x is the defect wurtzite structure, which well explains the experimental results. The passivation technique using crystalline SiN _x films would be promising for high-power and high-frequency applications of AlGaN/GaN HFETs.     

Microwave Dielectric Properties of BiCu<Subscript>2</Subscript>PO<Subscript>6</Subscript> Ceramics with Low Sintering Temperature

A BiCu₂PO₆ microwave dielectric ceramic was prepared using a solid-state reaction method. As the sintering temperature increased from 800°C to 880°C, the bulk density of BiCu₂PO₆ ceramic increased from 6.299 g/cm³ to 6.366 g/cm³; the optimal temperature was 860°C. The best microwave dielectric properties [permittivity (? _r ) = ～16, a quality factor (Q × f) = ～39,110 GHz and a temperature coefficient of resonant frequency (τ _f ) = ～?59 ppm/°C] were obtained in the ceramic sintered at 860°C for 2 h. Then, TiO₂ with a positive τ _f (～+400 ppm/°C) was added to compensate the τ _f value. The composite material was found to have a near-zero τ _f (+2.7 ppm/°C) and desirable microwave properties (? _r  = 19.9, Q × f = 24,885 GHz) when synthesized at a sintering temperature of 880°C. This system could potentially be used for low-temperature co-fired ceramics technology applications.     

Enhancement in Thermoelectric Properties of TiS<Subscript>2</Subscript> by Sn Addition

A series of Sn added TiS₂ (TiS₂:Sn _x ; x = 0, 0.05, 0.075 and 0.1) were prepared by solid state synthesis with subsequent annealing. The Sn atoms interacted with sulfur atoms in TiS₂ and formed a trace amount of misfit layer (SnS)_1+m(TiS_2?δ)_n compound with sulfur deficiency. A significant reduction in electrical resistivity with moderate decrease in the Seebeck coefficient was observed in Sn added TiS₂. Hence, a maximum power factor of 1.71 mW/m-K² at 373 K was obtained in TiS₂:Sn_0.05. In addition, the thermal conductivity was decreased with Sn addition and reached a minimum value of 2.11 W/m-K at 623 K in TiS₂:Sn_0.075, due to the impurity phase (misfit phase) and defects (excess Ti) scattering. The zT values increased from 0.08 in pristine TiS₂ to an optimized value of 0.46 K at 623 K in TiS₂:Sn_0.05.     

AC Electrical Conductivity of FeIn<Subscript>2</Subscript>Se<Subscript>4</Subscript> Single Crystals

The results obtained in a study of the frequency and temperature dependences of the ac electrical conductivity of FeIn₂Se₄ single crystals are presented. It is found that the law σ ~ f ^S (0.1 ≤ S ≤ 1.0) is obeyed for electrical conductivity in the 295–375 K temperature range at frequencies of 2 × 10⁴–10⁶ Hz. It shown that the frequency dependence of the conductivity in an FeIn₂Se₄ single crystal can be accounted for in terms of the multiplet model, and, consequently, the conductivity in these single crystals is characterized by the band-hopping mechanism.     

Electrical and photoelectric properties of <Emphasis Type="Italic">n</Emphasis>-TiN/<Emphasis Type="Italic">p</Emphasis>-Hg<Subscript>3</Subscript>In<Subscript>2</Subscript>Te<Subscript>6</Subscript> heterostructures

n-TiN/p-Hg₃In₂Te₆ heterostructures are fabricated by depositing a thin n-type titanium nitride (TiN) film onto prepared p-type Hg₃In₂Te₆ plates using reactive magnetron sputtering. Their electrical and photoelectric properties are studied. Dominant charge-transport mechanisms under forward bias are analyzed within tunneling-recombination and tunneling models. The fabricated n-TiN/p-Hg₃In₂Te₆ structures have the following photoelectric parameters at an illumination intensity of 80 mW/cm²: the open-circuit voltage is V_OC = 0.52 V, the short-circuit current is I_SC = 0.265 mA/cm², and the fill factor is FF = 0.39.     

Low-temperature instabilities of the electrical properties of Cd<Subscript>0.96</Subscript>Zn<Subscript>0.04</Subscript>Te:Cl semi-insulating crystals

The electrical properties in the temperature range 295–430 K and low-temperature (4.2 K) photoluminescence of Cd_1?xZn_xTe:Cl semi-insulating crystals grown from melts with a variable impurity content (C _Cl ⁰ = 5 × 10¹⁷–1 × 10¹⁹ cm^?3) are investigated. Nonequilibrium processes leading to a decrease in carrier concentration are observed in all the samples at low temperatures (T = 330–385 K). These changes are reversible. The activation energy of these processes E _a is found to be 0.88 eV. As with semi-insulating CdTe:Cl, the observed phenomena can be explained by a change in the charge state of background copper atoms: Cu_Cd ? Cu_i. The introduction of Zn changes the ratio of the concentrations of shallow-level donors Cu_i and Cl_Te from their levels in the initial material.     

Electrical properties of the <Emphasis Type="Italic">p</Emphasis><Superscript>+</Superscript>-Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>-<Emphasis Type="Italic">p</Emphasis>-GaSe isotype heterostructure

Electrical properties of a p⁺-Bi₂Te₃-p-GaSe isotype heterostructure fabricated for the first time are reported. A qualitative model is suggested which explains the emergence of negative differential conductivity for a forward-biased structure and for a reverse-biased structure, which is also illuminated.     

SiO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> layer formation during plasma sputtering of Si and SiO<Subscript>2</Subscript> targets

Deposition of SiO _x layers of variable composition onto silicon wafers was performed by co-sputtering of spaced Si and SiO₂ targets in argon plasma. Coordinate dependences of the thickness and refractive index of separately deposited Si and SiO₂ layers and the SiO _x layer grown during co-sputtering of targets were determined using optical techniques. It was shown that the SiO _x layer composition is not equal to a simple sum of thicknesses of separately deposited Si and SiO₂ layers. The coordinate dependences of the Si and SiO₂ layer thicknesses were calculated. To fit the calculated and experimental data, it is necessary to assume that no less than 10% of silicon is converted to dioxide during co-sputtering. A comparison of the coordinate dependences of the IR absorbance in SiO₂ and SiO _x layers with experimental ellipsometric data confirmed the presence of excess oxygen in the SiO _x layer. Taking into account such partial oxidation of sputtered silicon, composition isolines in the substrate plane were calculated. After annealing of the SiO _x layer at 1200°C, photoluminescence was observed in a wafer area predicted by calculations, which was caused by the formation of quantum-size Si nanocrystallites. The photoluminescence intensity was maximum at x = 1.78 ± 0.3, which is close to the composition optimum for ion-beam synthesis of nanocrystals.