Electronic and thermoelectric properties of Mg_2Ge_xSn-_(1-x)(x=0.25,0.50,0.75) solid solutions by first-principles calculations

The electronic structure and thermoelectric(TE) properties of Mg_2Ge_xSn_(1-x)(x = 0.25, 0.50, 0.75) solid solutions are investigated by first-principles calculations and semi-classical Boltzmann theory. The special quasi-random structure(SQS) is used to model the solid solutions, which can produce reasonable band gaps with respect to experimental results.The n-type solid solutions have an excellent thermoelectric performance with maximum zT values exceeding 2.0, where the combination of low lattice thermal conductivity and high power factor(PF) plays an important role. These values are higher than those of pure Mg_2Sn and Mg_2Ge. The p-type solid solutions are inferior to the n-type ones, mainly due to the much lower PF. The maximum zT value of 0.62 is predicted for p-type Mg_2Ge_(0.25)Sn_(0.75) at 800K. The results suggest that the n-type Mg_2Ge_xSn_(1-x) solid solutions are promising mid-temperature TE materials.     

Advances in thermoelectric (GeTe)x(AgSbTe2)100-x

The (GeTe)_x(AgSbTe₂)_100-x alloys, also called TAGS-x in short, have long been demonstrated as a promising candidate for thermoelectric applications with successful services as the p-type leg in radioisotope thermoelectric generators for space missions. This largely stems from the complex band structure for a superior electronic performance and strong anharmonicity for a low lattice thermal conductivity. Utilization of the proven strategies including carrier concentration optimization, band and defects engineering, an extraordinary thermoelectric figure of merit, zT, has been achieved in TAGS-based alloys. Here, crystal structure, band structure, microstructure, synthesis techniques and thermoelectric transport properties of TAGS-based alloys, as well as successful strategies for manipulating the thermoelectric performance, are surveyed with opportunities for further advancements. These strategies involved are believed to be in principle applicable for advancing many other thermoelectrics.     

Electronic structures and thermoelectric properties of solid solutions CuGa_(1-x) In_xTe_2 : A first-principles study

The electronic structures of solid solutions CuGal_xlnxTe2 are systematically investigated using the full-potential all-electron linearized augmented plane wave method. The calculated lattice parameters almost linearly increase with the increase of the In composition, which are in good agreement with the available experimental results. The calculated band structures with the modified Becke-Johnson potential show that all solid solutions are direct gap conductors. The band gap decreases linearly with In composition increasing. Based on the electronic structure calculated, we investigate the thermoelectric properties by the semi-classical Boltzmann transport theory. The results suggest that when Ga is replaced by In, the bipolar effect of Seebeck coefficient S becomes very obvious. The Seebeck coefficient even changes its sign from positive to negative for p-type doping at low carrier concentrations. The optimal p-type doping concentrations have been estimated based on the predicted maximum values of the power factor divided by the scattering time.     

Ab‐initio thermodynamic calculations of Mg2BIV (BIV = Si,Ge, Sn) solid solutions

The thermodynamic properties of ternary Mg₂B^IV (B^IV = Si, Ge, Sn) solid solutions were first calculated by the ab‐initio density functional method. The results showed that there exist composition regions with d²G /dx² < 0 in Mg₂Si_1–x Sn_x and Mg₂Ge_1–x Sn_x systems, implying the possibility of spinodal decomposition of the pseudobinary solid solutions. It is suggested that the spinodal decomposition would be a potential way to obtain Mg₂B^IV based bulk in‐situ nanocomposites with reduced grain sizes and enhanced phonon scattering, and hence an improved thermoelectric figure of merit. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Transport properties of Mg2 X 0.4Sn0.6 solid solutions (X = Si, Ge) with p-type conductivity

The transport properties of Mg₂ X _0.4Sn_0.6 (X = Si, Ge) solid solutions are investigated. It is shown that these materials can be rendered p-type with a hole concentration of up to 4 × 10¹⁹ cm^?3. The Hall coefficient, thermopower, and electrical conductivity are measured over a wide temperature range. The mobility of holes in these solid solutions is less than that of electrons by a factor of 2 for Mg₂Si_0.4Sn_0.6 and by a factor of 1.5 for Mg₂Ge_0.4Sn_0.6. Solid solutions in the Mg₂Ge-Mg₂Sn system appear more promising for thermoelectric applications.     

Strong renormalization of phonon frequencies in Mg(1-x)Al(x)B2

The phonon spectrum of Mg(1-x)Al(x)B2 shows a strong dependence on the aluminum content x. This is experimentally demonstrated by both Raman and inelastic neutron scattering and theoretically predicted by first-principles calculations. The observed changes in the phonon spectrum are put into perspective with respect to the superconducting properties within this family of materials.     

Evolution of magnetic properties in the normal spinel solid solution Mg(1-x)Cu(x)Cr2O4

We examine the evolution of magnetic properties in the normal spinel oxides Mg(1-x)Cu(x)Cr2O4 using magnetization and heat capacity measurements. The end-member compounds of the solid solution series have been studied in some detail because of their very interesting magnetic behavior. MgCr2O4 is a highly frustrated system that undergoes a first-order structural transition at its antiferromagnetic ordering temperature. CuCr2O4 is tetragonal at room temperature as a result of Jahn-Teller active tetrahedral Cu2+ and undergoes a magnetic transition at 135 K. Substitution of magnetic cations for diamagnetic Mg2+ on the tetrahedral A site in the compositional series Mg(1-x)Cu(x)Cr2O4 dramatically affects magnetic behavior. In the composition range 0 ≤ x ≤ ≈0.3, the compounds are antiferromagnetic. A sharp peak observed at 12.5 K in the heat capacity of MgCr2O4 corresponding to a magnetically driven first-order structural transition is suppressed even for small x. Uncompensated magnetism--with open magnetization loops--develops for samples in the x range ≈0.43 ≤ x ≤ 1. Multiple magnetic ordering temperatures and large coercive fields emerge in the intermediate composition range 0.43 ≤ x ≤ 0.47. The Néel temperature increases with increasing x across the series while the value of the Curie-Weiss Θ(CW) decreases. A magnetic temperature-composition phase diagram of the solid solution series is presented.     

Electrophysical and photoelectric properties of (CdSe)1−x(CuInSe2)x solid solutions

The results are given of measurements of the electrophysical properties in the interval of temperatures 300–900°K and of the photoelectric properties at 300°K of (CdSe)_1–x–(CuInSe₂)_x solid solutions. It is shown that the electrophysical and photoelectric properties of the solid solutions depend on the composition and temperature. The forbidden-band widths calculated from the temperature dependence of the conductivity and from the photoconductivity spectrum, respectively, vary from 1.68 and 1.77 eV for initial compound CdSe to 1.25 and 1.18 eV for the solid solution Cu_0.1Cd_0.9In_0.1Se_1.1.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 1, pp. 41–43, January, 1992.     

First-principles calculation of alloy scattering in Ge(x)Si(1-x)

First-principles electronic structure methods are used to find the rates of intravalley and intervalley n-type carrier scattering due to alloy disorder in Si(1-x)Ge(x) alloys. The required alloy scattering matrix elements are calculated from the energy splitting of nearly degenerate Bloch states which arises when one average host atom is replaced by a Ge or Si atom in supercells containing up to 128 atoms. Scattering parameters for all relevant Delta and L intravalley and intervalley alloy scattering are calculated. Atomic relaxation is found to have a substantial effect on the scattering parameters. f-type intervalley scattering between Delta valleys is found to be comparable to other scattering channels. The n-type carrier mobility, calculated from the scattering rate using the Boltzmann transport equation in the relaxation time approximation, is in excellent agreement with experiments on bulk, unstrained alloys.     

Application of the solid solution Cd(x)Hg(1-x)Ga(2)S(4) as a nonlinear optical crystal

We review the optical properties of the mixed crystal Cd(x)Hg(1-x)Ga(2)S(4) , propose three potential applications to which various physical properties can be tailored, and present experimental results of femtosecond optical parametric amplification in the mid IR from 5.5 to 8mum with 1.25-mum pumping by a 1-kHz Cr:forsterite regenerative amplifier.     

Splitting of the phase transition in ferroelectric solid solutions Sn2P2(SexS1−x)6 at high pressures

The influence of the temperature and hydrostatic pressure on the forbidden band width and dielectric permittivity of the ferroelectric solid solutions Sn₂P₂(Se_xS_1–x)₆ (x=0.04, 0.20, 0.30) is investigated. A change in the species and splitting of ferroelectric phase transition lines are detected for p = 0.140 and 0.026 GPa, respectively, for the solid solutions Sn₂P₂(Se_0.04S_0.96)₆ and Sn₂P₂(Se_0.20S_{0.80 6}, which is due to the existence of a Lifshits critical point separating the transitions into codimensional and noncodimensional phases on the p, T diagram. Shift coefficients with the pressure of the phase transition temperature are found for the solid solutions investigated.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 28–32, February, 1988.     

Influence of Ir substitution on the thermoelectric properties of Ba0.3(IrxCo1-x)4Sb12 solid solutions

Polycrystalline skutterudite solid solutions, Ba_0.3 (Ir_xCo_1-x)₄Sb₁₂ (x from 0 to 0.11), have been synthesized by a two-step solid state reaction method and sintered by a spark plasma sintering (SPS) technique. The influence of Ir substitution on electrical and thermal transport properties has been investigated in the temperature range of 300–850 K. Through Ir substitution, the lattice thermal conductivity was depressed due to the phonon scattering by point defects. The thermopower and thermoelectric power factor increased because of the enhancement of carrier acoustic lattice scattering especially at lower temperatures. Both the dimensionless figure of merit (ZT) and the thermoelectric compatibility factor (C_F), which play very important roles for applications, were improved over the whole temperature region. PACS 72.15.Eb; 72.15.Jf; 72.20.Pa; 63.20.Mt; 74.25.Fy An erratum to this article can be found at     

Electron delocalization enhances the thermoelectric performance of misfit layer compound (Sn1-xBixS)1.2(TiS2)2

The misfit layer compound (SnS)_1.2(TiS₂)₂ is a promising low-cost thermoelectric material because of its low thermal conductivity derived from the superlattice-like structure. However, the strong covalent bonds within each constituent layer highly localize the electrons thereby it is highly challenging to optimize the power factor by doping or alloying. Here, we show that Bi doping at the Sn site markedly breaks the covalent bonds networks and highly delocalizes the electrons. This results in a high charge carrier concentration and enhanced power factor throughout the whole temperature range. It is highly remarkable that Bi doping also significantly reduces the thermal conductivity by suppressing the heat conduction carried by phonons, indicating that it independently modulates phonon and charge transport properties. These effects collectively give rise to a maximum ZT of 0.3 at 720 K. In addition, we apply the single Kane band model and the Debye-Callaway model to clarify the electron and phonon transport mechanisms in the misfit layer compound (SnS)_1.2(TiS₂)₂.     

Molecular bonding in the conduction states of the Mg2X (X=Si,Ge, Sn) semiconductors

Summary The chemical bond in the electron-deficient semiconductor series Mg₂X (X=Si, Ge, Sn) is analysed in the pseudopotential self-consistent local-density scheme. Hard-core atomic potentials are used to investigate the physical properties of these compounds and to show the regularities peculiar to the periodic table. The ionic character of these materials is studied and related to the scaling electronegativities of their anions. Our results, in good agreement with the experiment, are discussed in order to explain the molecular behaviour of the bonding conduction states.

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Riassunto Si studia il legame chimico nella serie dei semiconduttori mancanti di elettroni Mg₂X, dove X=Si, Ge e Sn, con il metodo dello pseudopotenziale autocoerente nello schema del funzionale densità locale. Le proprietà fisiche dei composti in esame sono studiate utilizzando potenziali atomici che permettono di evidenziarne le caratteristiche di periodicità. Il carattere ionico di questi materiali è correlato all'elettronegatività degli anioni. I nostri risultati, in buon accordo con l'esperimento, sono discussi in modo da spiegare il comportamento molecolare degli stati di conduzione.

     

Pecularities of EPR spectra of the Gd impurity in the Sn-Rich Pb1−x Sn x Te(Gd) solid solutions

An electron paramagnetic resonance (EPR) experimental study of crystalline and powder p-Pb_1?x?y Sn _y Gd _y Te samples for various matrix compositionx and Gd contenty has been carried out. The study reveals that grinding the crystals into powder as well as their low-temperature annealing turns Gd impurity ions from the EPR-silent Gd²⁺ state to the EPR-active Gd³⁺ state, whereas high-temperature annealing in vacuum quenches EPR signals from Gd³⁺ ions. The experimental results are interpreted in terms of a model assuming that the trivalent charge state of the Gd impurity ions in lead and tin tellurides is a component part of the “substituting Gd impurity-Te vacancy” complex.     

The thermoelectric efficiency of CdSb and solid solutions of Zn x Cd1−x Sb with hole conductivity

Based on the study of transport effects in CdSb single crystals and solid solutions of ZnSb-CdSb with hole conductivity, an analysis of the thermoelectric conversion efficiency is made. The parameters, experimentally determined over a wide temperature range, are compared to the transport coefficients of a highly doped CdSb and solid solution of Zn_0.2Cd_0.8Sb.     

Magnetic excitations in EuCu(2)(Si(x)Ge(1-x))(2): from mixed valence towards magnetism

We report the inelastic neutron scattering study of spin dynamics in EuCu(2)(Si(x)Ge(1-x))(2) (x?=?1, 0.9, 0.75, 0.6), performed in a wide temperature range. At x?=?1 the magnetic excitation spectrum was found to be represented by the double-peak structure well below the energy range of the Eu(3+) spin-orbit (SO) excitation (7)F(0)→(7)F(1), so that at least the high-energy spectral component can be assigned to the renormalized SO transition. Change of the Eu valence towards 2?+ with increased temperature and/or Ge concentration results in further renormalization (lowering the energy) and gradual suppression of both inelastic peaks in the spectrum, along with developing sizeable quasielastic signal. The origin of the spectral structure and its evolution is discussed in terms of excitonic model for the mixed valence state.     

Room temperature oxidation of Cu(3)Ge films grown on Si and Si(1-x)Ge(x) substrates

Room temperature oxidation of Cu3Ge films grown on Si, Si(0.85)Ge(0.15) and Si(0.52)Ge(0.48) substrates, respectively, at a temperature of 200-300 degrees C was studied using transmission electron microscopy (TEM) in conjunction with energy dispersive spectrometry (EDS) and scanning electron microscopy (SEM). For Cu(3)Ge films grown at 200 degrees C and subsequently exposed in air for 1 week oxide protrusions and oxide networks appeared in the film surface and grain boundaries of Cu(3)Ge, respectively. At room temperature O from air and Si from the substrate, diffused along the grain boundaries of Cu(3)Ge to react with Cu(3)Ge grains, initiating the Cu(3)Si-catalyzed oxidation. Cu(3)Ge films are superior to Cu(3)(Si(1-x)Gex) films in retarding Cu(3)Si-catalyzed oxidation. Annealing at 300 degrees C allowed Si diffusion from the substrate into the Cu(3)Ge overlayer to form Cu(3)(Si(1-x)Gex), enhancing the Cu(3)Si-catalyzed oxidation rate. In the present study, Cu(3)Ge films grown on Si(0.52)Ge(0.48) at 200 degrees C show the best resistance to room temperature oxidation because higher Ge concentration in the substrate and lower temperature annealing can more effectively retard Si diffusion from the substrate into the Cu(3)Ge overlayer, and hence reduce the Cu(3)Si-catalyzed oxidation rate.