Pb<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Sn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te Alloys: Application Considerations

The search for alternative energy sources is at the forefront of applied research. In this context, thermoelectricity, i.e., direct conversion of thermal into electrical energy, plays an important role, particularly for exploitation of waste heat. Materials for such applications should exhibit thermoelectric potential and mechanical stability. PbTe-based compounds include well-known n-type and p-type compounds for thermoelectric applications in the 50°C to 600°C temperature range. This paper is concerned with the mechanical and transport properties of p-type Pb_0.5Sn_0.5Te:Te and PbTe<Na> samples, both of which have a hole concentration of ∼1 × 10²⁰ cm⁻³. The ZT values of PbTe<Na> were found to be higher than those of Pb_0.5Sn_0.5Te:Te, and they exhibited a maximal value of 0.8 compared with 0.5 for Pb_0.5Sn_0.5Te:Te at 450°C. However, the microhardness value of 49 H_V found for Pb_0.5Sn_0.5Te:Te was closer to that of the mechanically stable n-type PbTe (30 H_V) than to that of PbTe<Na> (71 H_V). Thus, although lower ZT values were obtained, from a mechanical point of view Pb_0.5Sn_0.5Te:Te is preferable over PbTe<Na> for practical applications.     

Metal-insulator transition in chromium-doped Pb<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ge<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te alloys

The electrical properties of chromium-doped n-Pb_1?x Ge _x Te alloys (x = 0.02–0.13) have been studied. A decrease in the free-electron concentration and a metal-insulator transition are observed as the germanium content of alloys increases. This is due to the Fermi level pinning by the chromium impurity level and to the flow of electrons from the conduction band to the impurity level. The experimental data obtained are used to calculate, in terms of the two-band Kane dispersion law, the dependences of the electron concentration and Fermi energy on the germanium content in the alloy. The motion rate of the chromium-related level with respect to the conduction band bottom is determined and a model of variation of the electronic structure with the matrix composition is suggested.     

Pb<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Sn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te epitaxial films for terahertz detectors

Liquid-phase epitaxy is used to fabricate Pb_0.8Sn_0.2Te films, undoped or doped with indium to different levels. The depth profiles of the carrier density and dopant concentration in the films are measured and examined. A uniform dopant concentration to a depth of 15 μm is obtained. Electrical-conduction inversion is observed at a temperature of 77.3 K as the doping level is varied. The liquid-phase epitaxial method is shown to be a more suitable technology for the reproducible manufacture of epitaxial films with a given carrier density, such as the ones used in terahertz detectors.     

Radiative recombination channels in Si/Si<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ge<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> nanostructures

Using the solution of the 2D Schrödinger equation, systematic features of distribution of charge carriers in the Si/Si_{1 ? x} Ge _x nanostructures and variations in the efficiency of radiative recombination when pyramidal 2D clusters are transformed into 3D dome clusters with increasing thickness of nanolayers are established. The effect of the composition of the layers on the efficiency of the elastic stress in the structure and, as a consequence, the variation in conduction bands and valence band of the Si_{1 ? x} Ge _x nanostructures is taken into account. On realization of the suggested kinetics model, which describes recombination processes in crystalline structures, saturation of radiation intensity with increasing the pump intensity caused by an increase in the contribution of the Auger recombination is observed. A decrease in the contribution of the nonradiative Auger recombination is attained by decreasing the injection rate of carriers into the clusters, and more precisely, by an increase in the cluster concentration and an increase in the rate of radiative recombination.     

Electron spin resonance in Cd<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>x</Subscript>Te and Zn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>x</Subscript>Te compounds

Electron spin resonance in semimagnetic Cd_1?xMn_xTe (0<x<0.7) and Zn_1?xMn_xTe (0<x<0.53) compounds was studied at temperatures of 77 and 300 K. It is found that two types of paramagnetic centers exist in Zn_1?xMn_xTe, one of which is related to Mn²⁺ ions and the other is attributed to structural defects in the crystals.     

Thermoelectric Properties and Electronic Structure of Bi- and Ag-Doped Mg<Subscript>2</Subscript>Si<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ge<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Compounds

Mg₂Si_1−x Ge _x compounds were prepared from pure elements by melting in tantalum crucibles. The reaction was conducted under an inert gas in a special laboratory setup. Samples for thermoelectric measurements were formed by hot pressing. Structure and phase composition of the obtained materials were investigated by x-ray diffraction (XRD). Morphology and chemical composition were examined by scanning electron microscopy (SEM) and energy-dispersive x-ray spectroscopy (EDS), respectively. Thermoelectric properties, i.e., the Seebeck coefficient, the electrical conductivity, and the thermal conductivity, were measured in the temperature range of 500 K to 900 K. The effect of Bi and Ag doping on the thermoelectric performance of Mg-Si-Ge ternary compounds was investigated. The electronic structures of binary compounds were calculated using the Korringa–Kohn–Rostoker (KKR) method. The effects of disorder, including Ge substitution and Bi or Ag doping, were accounted for in the KKR method with coherent potential approximation calculations. The thermoelectric properties of doped Mg₂Si_1−x Ge _x are discussed with reference to computed density of states as well as the complex energy band structure.     

Electronic and structural transitions in Pb<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ge<Subscript>x</Subscript>Te:Ga alloys under pressure

The effect of pressure on electrical properties of Ga-doped n-Pb_1?xGe_xTe alloys (x=0.06, 0.08) is studied. The pressure dependence of the activation energy of a deep Ga impurity center is obtained. It is shown that the position of the Ga level with respect to the bottom of the conduction band is virtually unchanged under pressure. Anomalies are found in the temperature and pressure dependences of the resistivity; these anomalies are apparently associated with structural phase transitions from the cubic to the rhombohedral and orthorhombic phases, respectively. The results obtained are used to construct a diagram of the modification of the energy spectrum of charge carriers in the cubic phase of the alloys investigated under pressure.     

Cathodoluminescence from dilute GaN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>As<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript> solutions (<Emphasis Type="Italic">x</Emphasis> ≤ 0.03)

Cathodoluminescence from GaN _x As_1?x layers (0 ≤ x ≤ 0.03) was measured at photon energies ranging from the intrinsic absorption edge to 3 eV at room temperature. An additional emission band was visible in the visible range of the cathodoluminescence spectra. The intensity of this band is two orders of magnitude lower than the edge-emission intensity. The photon energy corresponding to the peak of this band and its FWHM are virtually independent of x and equal to ～2.1 and 0.6–0.7 eV, respectively. This emission is related to indirect optical transitions of electrons from the L _6c and Δ conduction-band minimums to the Γ₁₅ valence-band maximum.     

Structure and Thermoelectric Properties of Te- and Ge-Doped Skutterudites CoSb<Subscript>2.875−<Emphasis Type="Italic">x</Emphasis></Subscript>Ge<Subscript>0.125</Subscript>Te<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

n-Type CoSb_2.875−x Ge_0.125Te _x (x = 0.125 to 0.275) compounds with different Te contents have been synthesized by a melt–quench–anneal–spark plasma sintering method, and the effects of Te content on the structure and thermoelectric properties have been investigated. The results show that all specimens exhibited n-type conduction characteristics. The solubility limit of Te in CoSb_2.875−x Ge_0.125Te _x is found to be x = 0.25. The solubility of Te in CoSb₃ is increased through charge compensation of the element Ge. The room-temperature carrier concentration N _p of CoSb_2.875−x Ge_0.125Te _x skutterudites increases with increasing Te content, and the compounds possess high power factors. The maximum power factor of 3.89 × 10⁻³ W m⁻¹ K⁻² was obtained at 720 K for the CoSb_2.625Ge_0.125Te_0.25 compound. The thermal conductivity decreases dramatically with increasing Te content due to strong point defect scattering. The maximum value of the thermoelectric figure of merit ZT = 1.03 was obtained at 800 K for CoSb_2.625Ge_0.125Te_0.25, benefiting from a lower thermal conductivity and a higher power factor. The figure of merit is competitive with values reported for single-filled skutterudites.     

Photosensitivity of Pb<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Sn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te:In films in the region of intrinsic absorption

The steady-state photocurrent in the fundamental absorption region of Pb_{1 ? x} Sn _x Te:In films is calculated with the field injection of electrons from the contact and their capture by traps in the bulk taken into account. The calculated and experimental current-voltage characteristics are compared at liquid-helium temperature. The represented experimental data on the dependence of the Hall effect on the injection level agree well with the considered model.     

Compositional and Strain Characterization of Ion-Beam-Synthesized Ge<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Si<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript> Thin Films

A thin film of Ge-rich Ge _x Si_1−x on a (100) Si substrate was synthesized by ion implantation followed by thermal oxidation. Proper oxidation conditions were maintained to produce a film with Ge atomic content of more than 95%, confirmed by both high-resolution Rutherford backscattering spectrometry (RBS) and Raman spectroscopy. The strain state of the Ge-rich thin film is a function of its thickness, as determined by the implantation fluence. The use of Raman spectroscopy to monitor the composition and strain state of the Ge thin film formed is discussed.     

Influence of samarium on the thermoelectric figure of merit of Sm<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Pb<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Te alloys

The temperature and concentration dependences of the electrical (conductivity σ, the Hall coefficient R), thermoelectric (thermovoltage α), and thermal (thermal conductivity K _tot) characteristics of Sm _x Pb_{1 − x} Te alloys (x = 0, 0.02, 0.04, 0.08) are studied in the temperature range 100–500 K. Using the data for σ, α, and K _tot, the thermoelectric power α²σ, figure of merit Z, and efficiency δ are calculated. It is established that at room-temperature α²σ and Z peak at the hole concentration p ≈ 1.2 × 10¹⁸ cm⁻³.     

Investigation of Multicarrier Transport in LPE-Grown Hg<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te Layers

A detailed study is presented of multicarrier transport properties in liquid-phase epitaxy (LPE)-grown n-type HgCdTe films using advanced mobility spectrum analysis techniques over the temperature range from 95 K to 300 K. Three separate electron species were identified that contribute to the total conduction, and the temperature-dependent characteristics of carrier concentration and mobility were extracted for each individual carrier species. Detailed analysis allows the three observed contributions to be assigned to carriers located in the bulk long-wave infrared (LWIR) absorbing layer, the wider-gap substrate/HgCdTe transition layer, and a surface accumulation layer. The activation energy of the dominant high-mobility LWIR bulk carrier concentration in the high temperature range gives a very good fit to the Hansen and Schmit expression for intrinsic carrier concentration in HgCdTe with a bandgap of 172 meV. The mobility of these bulk electrons follows the classic μ ~ T ^−3/2 dependence for the phonon scattering regime. The much lower sheet densities found for the other two, lower-mobility electron species show activation energies of the order of ~20 meV, and mobilities that are only weakly dependent on temperature and consistent with expected values for the wider-bandgap transition layer and a surface accumulation layer.     

Photoluminescence of Hg<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te based heterostructures grown by molecular-beam epitaxy

Photoluminescence (PL) of Hg_{1 − x} Cd _x Te-based heterostructures grown by molecular-beam epitaxy (MBE) on GaAs and Si substrates has been studied. It is shown that a pronounced disruption of the long-range order in the crystal lattice is characteristic of structures of this kind. It is demonstrated that the observed disordering is mostly due to the nonequilibrium nature of MBE and can be partly eliminated by postgrowth thermal annealing. Low-temperature spectra of epitaxial layers and structures with wide potential wells are dominated by the recombination peak of an exciton localized in density-of-states tails; the energy of this peak is substantially lower than the energy gap. In quantum-well (QW) structures at low temperatures, the main PL peak is due to carrier recombination between QW levels and the energy of the emitted photon is strictly determined by the effective (with the QW levels taken into account) energy gap.     

Electrodeposition of Bi<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Sb<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript>Te<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> Thermoelectric Films from DMSO Solution

The electrochemical behavior of nonaqueous dimethyl sulfoxide solutions of Bi^III, Te^IV, and Sb^III was investigated using cyclic voltammetry. On this basis, Bi _x Sb_2−x Te _y thermoelectric films were prepared by the potentiodynamic electrodeposition technique in nonaqueous dimethyl sulfoxide solution, and the composition, structure, morphology, and thermoelectric properties of the films were analyzed. Bi _x Sb_2−x Te _y thermoelectric films prepared under different potential ranges all possessed a smooth morphology. After annealing treatment at 200°C under N₂ protection for 4 h, all deposited films showed p-type semiconductor properties, and their resistances all decreased to 0.04 Ω to 0.05 Ω. The Bi_0.49Sb_1.53Te_2.98 thermoelectric film, which most closely approaches the stoichiometry of Bi_0.5Sb_1.5Te₃, possessed the highest Seebeck coefficient (85 μV/K) and can be obtained under potentials of −200 mV to −400 mV.     

Resonant gallium level in Pb<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Sn<Subscript>x</Subscript>Te alloys under pressure

The effect of pressure on electrical properties of the n-Pb_1?x Sn_xTe alloy (x = 0.21) doped with gallium is studied. A decrease in the free-electron concentration with increasing temperature and an increase in this concentration with increasing pressure are observed; these observations indicate that the Fermi level is pinned at the resonant gallium level. The two-band Kane’s dispersion law and experimental data were used to calculate the pressure dependences of the electron concentration and Fermi level. A diagram of transformation of the charge-carrier energy spectrum in Pb_1?x Sn_xTe:Ga subjected to pressure is suggested; the rate of the shift of the gallium resonant level in reference to the midgap under the effect of pressure is determined.     

Specific features of conductivity of Cd<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Zn<Subscript>x</Subscript>Te and Cd<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>x</Subscript>Te single crystals

The electrical characteristics of p-type Cd_1?xZn_xTe (x=0.05) and Cd_1?xMn_xTe (x=0.04) single crystals with a resistivity of 10³–10¹⁰ Ω cm at 300 K are studied. The conductivity and its variation with temperature are interpreted on the basis of statistics of electrons and holes in a semiconductor with deep acceptor impurities (defects), with regard to their compensation by donors. The depth of acceptor levels and the degree of their compensation are determined. The problems of attaining near intrinsic conductivity close to intrinsic are discussed.     

Influence of Composition on the Thermoelectric Properties of Bi<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Sb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Thin Films

Bi_1?x Sb _x solid solutions have attracted much attention as promising thermoelectric (TE) materials for cooling devices at temperatures below ～200 K and as unique model materials for solid-state science because of a high sensitivity of their band structure to changes in composition, temperature, pressure, etc. Earlier, we revealed a non-monotonic behavior of the concentration dependences of TE properties for polycrystalline Bi_1?x Sb _x solid solutions and attributed these anomalies to percolation effects in the solid solution, transition to a gapless state, and to a semimetal–semiconductor transition. The goal of the present work is to find out whether the non-monotonic behavior of the concentration dependences of TE properties is observed in the thin film state as well. The objects of the study are Bi_1?x Sb _x thin films with thicknesses in the range d = 250–300 nm prepared by thermal evaporation of Bi_1?x Sb _x crystals (x = 0–0.09) onto mica substrates. It was shown that the anomalies in the dependence of the TE properties on Bi_1?x Sb _x crystal composition are reproduced in thin films.     

Analysis of Carrier Transport in <Emphasis Type="Italic">n</Emphasis>-Type Hg<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te with Ultra-Low Doping Concentration

Mercury cadmium telluride (HgCdTe, or MCT) with low n-type indium doping concentration offers a means for obtaining high performance infrared detectors. Characterizing carrier transport in materials with ultra low doping (N_D?=?10¹⁴ cm^?3 and lower), and multi-layer material structures designed for infrared detector devices, is particularly challenging using traditional methods. In this work, Hall effect measurements with a swept B-field were used in conjunction with a multi-carrier fitting procedure and Fourier-domain mobility spectrum analysis to analyze multi-layered MCT samples. Low temperature measurements (77 K) were able to identify multiple carrier species, including an epitaxial layer (x?=?0.2195) with n-type carrier concentration of n?=?1?×?10¹⁴ cm^?3 and electron mobility of μ?=?280000 cm²/Vs. The extracted electron mobility matches or exceeds prior empirical models for MCT, illustrating the outstanding material quality achievable using current epitaxial growth methods, and motivating further study to revisit previously published material parameters for MCT carrier transport. The high material quality is further demonstrated via observation of the quantum Hall effect at low temperature (5 K and below).     

Injection currents in narrow-gap (Pb<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Sn<Subscript>x</Subscript>Te):In insulators

The low-temperature current-voltage characteristics of narrow-gap (Pb_1?xSn_xTe):In have been studied experimentally and calculated for a wide range of electric fields. It is shown that the obtained data are satisfactorily described in terms of a space-charge-limited current model in the presence of traps. The concentration and energy depth of the traps have been estimated.