Roles of Defects and Sb-Doping in the Thermoelectric Properties of Full-Heusler Fe2TiSn.

The potential of Fe2TiSn full-Heusler compounds for thermoelectric applications has been suggested theoretically, but not yet proven experimentally, due to the difficulty in obtaining reproducible, homogeneous, phase-pure and defect-free samples. In this work, we studied Fe2TiSn1-xSbx polycrystals (x from 0 to 0.6), fabricated by high-frequency melting and long-time high-temperature annealing. We obtained fairly good phase purity, a homogeneous microstructure, and good matrix stoichiometry. Although the intrinsic p-type transport behavior is dominant, n-type charge compensation by Sb-doping is demonstrated. Calculations of the formation energy of defects and electronic properties carried out using the density functional theory formalism reveal that charged iron vacancies VFe2- are the dominant defects responsible for the intrinsic p-type doping of Fe2TiSn under all types of (except Fe-rich) growing conditions. In addition, Sb substitutions at the Sn site give rise either to SbSn, SbSn1+, which are responsible for n-type doping and magnetism (SbSn) or to magnetic SbSn1-, which act as additional p-type dopants. Our experimental data highlight good thermoelectric properties close to room temperature, with Seebeck coefficients up to 56 µV/K in the x = 0.2 sample and power factors up to 4.8 × 10-4 W m-1 K-2 in the x = 0.1 sample. Our calculations indicate the appearance of a pseudogap under Ti-rich conditions and a large Sb-doping level, possibly improving further the thermoelectric properties.

Low-dimensional transport and large thermoelectric power factors in bulk semiconductors by band engineering of highly directional electronic states.

Thermoelectrics are promising for addressing energy issues but their exploitation is still hampered by low efficiencies. So far, much improvement has been achieved by reducing the thermal conductivity but less by maximizing the power factor. The latter imposes apparently conflicting requirements on the band structure: a narrow energy distribution and a low effective mass. Quantum confinement in nanostructures and the introduction of resonant states were suggested as possible solutions to this paradox, but with limited success. Here, we propose an original approach to fulfill both requirements in bulk semiconductors. It exploits the highly directional character of some orbitals to engineer the band structure and produce a type of low-dimensional transport similar to that targeted in nanostructures, while retaining isotropic properties. Using first-principle calculations, the theoretical concept is demonstrated in Fe2YZ Heusler compounds, yielding power factors 4 to 5 times larger than in classical thermoelectrics at room temperature. Our findings are totally generic and rationalize the search of alternative compounds with similar behavior. Beyond thermoelectricity, these might be relevant also in the context of electronic, superconducting, or photovoltaic applications.

Highly confined spin-polarized two-dimensional electron gas in SrTiO3/SrRuO3 superlattices.

We report first-principles characterization of the structural and electronic properties of (SrTiO3)5/(SrRuO3)1 superlattices. We show that the system exhibits a spin-polarized two-dimensional electron gas, extremely confined to the 4d orbitals of Ru in the SrRuO3 layer. Every interface in the superlattice behaves as a minority-spin half-metal ferromagnet, with a magnetic moment of µ=2.0µ(B)/SrRuO3 unit. The shape of the electronic density of states, half-metallicity, and magnetism are explained in terms of a simplified tight-binding model, considering only the t(2g) orbitals plus (i) the bidimensionality of the system and (ii) strong electron correlations.

Electroresistance effect in ferroelectric tunnel junctions with symmetric electrodes.

Understanding the effects that govern electronic transport in ferroelectric tunnel junctions (FTJs) is of vital importance to improve the efficiency of devices such as ferroelectric memories with nondestructive readout. However, our current knowledge (typically based on simple semiempirical models or first-principles calculations restricted to the limit of zero bias) remains partial, which may hinder the development of more efficient systems. For example, nowadays it is commonly believed that the tunnel electroresistance (TER) effect exploited in such devices mandatorily requires, to be sizable, the use of two different electrodes, with related potential drawbacks concerning retention time, switching, and polarization imprint. In contrast, here we demonstrate at the first-principles level that large TER values of about 200% can be achieved under finite bias in a prototypical FTJ with symmetric electrodes. Our atomistic approach allows us to quantify the contribution of different microscopic mechanisms to the electroresistance, revealing the dominant role of the inverse piezoelectric response of the ferroelectric. On the basis of our analysis, we provide a critical discussion of the semiempirical models traditionally used to describe FTJs.

Spontaneous 2-dimensional carrier confinement at the n-type SrTiO3/LaAlO3 interface.

We describe the intrinsic mechanism of 2-dimensional electron confinement at the n-type SrTiO3/LaAlO3 interface as a function of the sheet carrier density n(s) via advanced first-principles calculations. Electrons localize spontaneously in Ti 3d(xy) levels within a thin (≲2 nm) interface-adjacent SrTiO3 region for n(s) lower than a threshold value n(c)∼10(14) cm(-2). For n(s)>n(c) a portion of charge flows into Ti 3d(xz)-d(yz) levels extending farther from the interface. This intrinsic confinement can be attributed to the interface-induced symmetry breaking and localized nature of Ti 3d t(2g) states. The sheet carrier density directly controls the binding energy and the spatial extension of the conductive region. A direct, quantitative relation of these quantities with n(s) is provided.

R3Au(6+x)Al26T (R = Ca, Sr, Eu, Yb; T = early transition metal): a large family of compounds with a stuffed BaHg11 structure type grown from aluminum flux.

A collection of new quaternary intermetallic compounds with a cubic, stuffed BaHg(11) structure type has been synthesized by the combination of a divalent rare earth or alkaline earth metal R, an early transition metal T, and gold in an excess of molten aluminum. Structural characterization of these R(3)Au(6+x)Al(26)T compounds by powder and single crystal X-ray diffraction indicates that the unit cell varies with the radii of the early transition metal T and the rare earth/alkaline earth R as expected. The element T (where T = group 4, 5, 6, and 7 element) appears to be responsible for the stabilization of up to 43 different members of the R(3)Au(6+x)Al(26)T family of compounds. Varying amounts of disorder and trends in partial occupancies of the Au stuffed site--the site that is vacant in the parent compound BaHg(11)--are also indicated by the diffraction studies of this family of compounds. Magnetic susceptibility data reveals that the transition metal atoms in these materials do not possess local magnetic moments. For the magnetic rare earth containing materials, the europium compounds undergo a ferromagnetic transition at 10 K, and the ytterbium analogues show mixed valent behavior. Band structure calculations also support a mixed valent state for Yb in these compounds.

Intermetallic compounds with near Zintl phase behavior: RE2Zn3Ge6 (RE = La, Ce, Pr, Nd) grown from liquid indium.

A series of compounds has been discovered while investigating reactions of rare earth, transition metals, and Ge in excess indium. These compounds, RE2Zn3Ge6 (RE = La, Ce, Pr, Nd), are isostructural, crystallizing in the orthorhombic space group Cmcm with lattice parameters a = 5.9691(9) angstroms, b = 24.987(4) angstroms, and c = 5.9575(9) angstroms for La2Zn3Ge6, a = 5.9503(5) angstroms, b = 24.761(2) angstroms, and c = 5.9477(5) angstroms for the Ce analogue, a =5.938(2) angstroms, b = 24.708(8) angstroms, and c = 5.936(2) angstroms for Pr2Zn3Ge6, and a = 5.9094(7) angstroms, b = 24.619(3) angstroms, and c = 5.9063(5) angstroms for the Nd analogue. The structure is composed of PbO-like ZnGe layers and ZnGe4 cage layers and is related to the Ce4Zn8Ge(11-x) structure type. The bonding in the system can be rationalized using the Zintl concept resulting in a material that is expected to be a valence precise semiconductor, although its behavior is more consistent with it being a semimetal, making it an intermediate case. The results of band structure calculations and magnetic measurements of these compounds are discussed.

On the lamellar compounds CuBiP(2)Se(6), AgBiP(2)Se(6) and AgBiP(2)S(6). Antiferroelectric phase transitions due to cooperative Cu(+) and Bi(3+) ion motion.

CuBiP(2)Se(6), AgBiP(2)Se(6), and AgBiP(2)S(6) were prepared from the corresponding elements. CuBiP(2)Se(6) and AgBiP(2)Se(6) crystallize in the space group R with a = 6.5532(16) A and c = 39.762(13) A for CuBiP(2)Se(6) and a = 6.6524(13) A and c = 39.615(15) A for AgBiP(2)Se(6). AgBiP(2)S(6) crystallizes in the triclinic space group P with a = 6.3833(13) A, b = 7.1439(14) A, c = 9.5366(19) A, alpha = 91.89(3) degrees , beta = 91.45(3) degrees , gamma = 94.05(3) degrees . CuBiP(2)Se(6) was found to exhibit a temperature-dependent antiferroelectric ordering of the Cu(+) and Bi(3+) ions in the lattice. An intermediate and a fully ordered structure were refined at 173 and 97 K, respectively. Electronic band and total energy calculations at the DFT level clearly suggest that the antiferroelectric model is energetically favored over the paraelectric and hypothetical ferrielectric models. This phase transition can be classified as a second-order Jahn-Teller distortion. The antiferroelectric state of CuBiP(2)Se(6) is an indirect gap semiconductor. The compounds were characterized with differential thermal analysis and solid-state UV/vis diffuse reflectance spectroscopy. Generalized implications regarding the expected ferroelectric behavior of compounds in the CuMP(2)Se(6) system (M = trivalent metal) are discussed.

Tb4FeGe8 grown in liquid gallium: trans-cis chains from the distortion of a planar Ge square net.

The ternary germanide Tb4FeGe8 was obtained from Ga flux reactions. The crystal structure studied with single-crystal X-ray diffraction revealed the existence of an orthorhombic average substructure (Cmcm, Z=1) with cell parameters a = 4.1118(14) A, b=15.844(5) A, and c=3.9885(15) A. The refinement [I > 2sigma(I)] converged to final residuals R1/wR2 = 0.0363/0.0893. The average structure (CeNiSi2-type) consists of a 3D [Fe1/4Ge2] framework where Ge atoms form a square net and Fe atoms reside alternatively above and below it with only 1/4 occupation probability. X-ray and electron diffraction studies showed a modulation in the Ge net. The modulated structure was refined based on a 4-fold monoclinic supercell (P2(1)/n) with parameters a = 5.7315(11) A, b = 15.842(3) A, c = 11.438(2) A, and beta = 91.724(4) degrees with R1/wR2 = 0.0643/0.1735 and uncovered a severe distortion of the Ge square net. The Ge atoms are displaced to form an array of cis-trans chains. The Ge-Ge distances within these chains are distinctively bonding, whereas those between the chains are nonbonding. Results of the electronic structure calculations and magnetic measurements are also reported. The structural distortions found in Tb4FeGe8 cast a doubt onto the correctness of many of the reported REM1-xGe2 disordered compounds and call for reinvestigation.

Resonant states in the electronic structure of the high performance thermoelectrics AgPbmSbTe2+m: the role of Ag-Sb microstructures.

Ab initio electronic structure calculations based on gradient corrected density-functional theory were performed on a class of novel quaternary compounds AgPb(m)SbTe(2+m), which were found to be excellent high temperature thermoelctrics with a large figure of merit ZT approximately 2.2 at 800 K. We find that resonant states appear near the top of the valence and bottom of the conduction bands of bulk PbTe when Ag and Sb replace Pb. These states can be understood in terms of modified Te-Ag(Sb) bonds. The electronic structure near the gap depends sensitively on the microstructural arrangements of Ag-Sb atoms, suggesting that large ZT values may originate from the nature of these ordering arrangements.

V2Al5Ge5: first ternary intermetallic in the V-Al-Ge system accessible in liquid aluminium.

The intermetallic compound V2Al5Ge5 grown from Al flux is reported. V2Al5Ge5: orthorhombic, Cmcm, a = 5.4072(10), b = 12.978(2), and c = 11.362(2) A, the structure features distorted pentagonal prismatic columns defined by Al and Ge atoms. Vanadium atoms occupy the central axis of columns forming a chain with long-short alternation of V-V bonds. This compound is resistant to air oxidation up to 500 degrees C.

Intermetallics as zintl phases: Yb2Ga4Ge6 and RE3Ga4Ge6 (RE=Yb, Eu): structural response of a [Ga4Ge6]4- framework to reduction by two electrons.

Two new intermetallic compounds, Yb(2)Ga(4)Ge(6) and Yb(3)Ga(4)Ge(6), were obtained from reactions in molten Ga. A third compound, Eu(3)Ga(4)Ge(6), was produced by direct combination of the elements. The crystal structures of these compounds were studied by single-crystal X-ray diffraction. Yb(2)Ga(4)Ge(6) crystallizes in an orthorhombic cell with a=4.1698(7), b=23.254(4), c=10.7299(18) A in the polar space group Cmc2(1). The structure of RE(3)Ga(4)Ge(6) is monoclinic, space group C2/m, with cell parameters a=23.941(6), b=4.1928(11), c=10.918(3) A, beta=91.426(4) degrees for RE=Yb, and a=24.136(2), b=4.3118(4), c=11.017(1) A, beta=91.683(2) degrees for RE=Eu. The refinement [I>2 sigma(I)] converged to the final residuals R(1)/wR(2)=0.0229/0.0589, 0.0411/0.1114, and 0.0342/0.0786 for Yb(2)Ga(4)Ge(6), Yb(3)Ga(4)Ge(6), and Eu(3)Ga(4)Ge(6), respectively. The structures of these two families of compounds can be described by a Zintl concept of bonding, in which the three-dimensional [Ga(4)Ge(6)](n-) framework serves as a host and electron sink for the electropositive RE atoms. The structural relation of RE(3)Ga(4)Ge(6) to of Yb(2)Ga(4)Ge(6) lies in a monoclinic distortion of the orthorhombic cell of Yb(2)Ga(4)Ge(6) and reduction of the [Ga(4)Ge(6)] network by two electrons per formula unit. The results of theoretical calculations of the electronic structure, electrical transport data, and thermochemical and magnetic measurements are also reported.

Yb8Ge3Sb5, a metallic mixed-valent Zintl phase containing the polymeric 1 infinity[Ge3 4-] anions.

Yb8Ge3Sb5 is a nonclassical Zintl phase with metallic properties arising from the electropositive "spectator" cations of Yb. This compound contains the new Zintl anion 1infinity(Ge3)4- and is stabilized via a combination of Yb2+ and Yb3+ ions.

Impressive structural diversity and polymorphism in the modular compounds ABi3Q5 (A = Rb, Cs; Q = S, Se, Te).

An outstanding example of structural diversity and complexity is found in the compounds with the general formula ABi(3)Q(5) (A = alkali metal; Q = chalcogen). gamma-RbBi(3)S(5) (I), alpha-RbBi(3)Se(5) (II), beta-RbBi(3)Se(5) (III), gamma-RbBi(3)Se(5) (IV), CsBi(3)Se(5) (V), RbBi(3)Se(4)Te (VI), and RbBi(3)Se(3)Te(2) (VII) were synthesized from A(2)Q (A = Rb, Cs; Q = S, Se) and Bi(2)Q(3) (Q = S, Se or Te) at temperatures above 650 degrees C using appropriate reaction protocols. gamma-RbBi(3)S(5) and alpha-RbBi(3)Se(5) have three-dimensional tunnel structures while the rest of the compounds have lamellar structures. gamma-RbBi(3)S(5), gamma-RbBi(3)Se(5), and its isostructural analogues RbBi(3)Se(4)Te and RbBi(3)Se(3)Te(2) crystallize in the orthorhombic space group Pnma with a = 11.744(2) A, b = 4.0519(5) A, c = 21.081(3) A, R1 = 2.9%, wR2 = 6.3% for (I), a = 21.956(7) A, b = 4.136(2) A, c = 12.357(4) A, R1 = 6.2%, wR2 = 13.5% for (IV), and a = 22.018(3) A, b = 4.2217(6) A, c = 12.614(2) A, R1 = 6.2%, wR2 = 10.3% for (VI). gamma-RbBi(3)S(5) has a three-dimensional tunnel structure that differs from the Se analogues. alpha-RbBi(3)Se(5) crystallizes in the monoclinic space group C2/m with a = 36.779(4) A, b = 4.1480(5) A, c = 25.363(3) A, beta = 120.403(2) degrees, R1 = 4.9%, wR2 = 9.9%. beta-RbBi(3)Se(5) and isostructural CsBi(3)Se(5) adopt the space group P2(1)/m with a = 13.537(2) A, b = 4.1431(6) A, c = 21.545(3) A, beta = 91.297(3) degrees, R1 = 4.9%, wR2 = 11.0% for (III) and a = 13.603(3) A, b = 4.1502(8) A, c = 21.639(4) A, beta = 91.435(3) degrees, R1 = 6.1%, wR2 = 13.4% for (V). alpha-RbBi(3)Se(5) is also three-dimensional, whereas beta-RbBi(3)Se(5) and CsBi(3)Se(5) have stepped layers with alkali metal ions found disordered in several trigonal prismatic sites between the layers. In gamma-RbBi(3)Se(5) and RbBi(3)Se(4)Te, the layers consist of Bi(2)Te(3)-type fragments, which are connected in a stepwise manner. In the mixed Se/Te analogue, the Te occupies the chalcogen sites that are on the "surface" of the layers. All compounds are narrow band-gap semiconductors with optical band gaps ranging 0.4-1.0 eV. The thermal stability of all phases was studied, and it was determined that gamma-RbBi(3)Se(5) is more stable than the and alpha- and beta-forms. Electronic band calculations at the density functional theory (DFT) level performed on alpha-, beta-, and gamma-RbBi(3)Se(5) support the presence of indirect band gaps and were used to assess their relative thermodynamic stability.

RE2MAl6Si4 (RE = Gd, Tb, Dy; M = Au, Pt): layered quaternary intermetallics featuring CaAl2Si2-type and YNiAl4Ge2-type slabs grown from aluminum flux.

Six new intermetallic aluminum silicides--Gd(2)PtAl(6)Si(4), Gd(2)AuAl(6)Si(4), Tb(2)PtAl(6)Si(4), Tb(2)AuAl(6)Si(4), Dy(2)PtAl(6)Si(4), and Dy(2)AuAl(6)Si(4)--have been obtained from reactions carried out in aluminum flux. The structure of these compounds was determined by single-crystal X-ray diffraction. They form in space group Rthremacr;m with cell constants of a = 4.1623(3) A and c = 51.048(5) A for the Gd(2)PtAl(6)Si(4) compound. The crystal structure is comprised of hexagonal nets of rare earth atoms alternating with two kinds of layers that have been observed in other multinary aluminide intermetallic compounds (CaAl(2)Si(2) and YNiAl(4)Ge(2)). All six RE(2)MAl(6)Si(4) compounds show antiferromagnetic transitions at low temperatures (T(N) < 20 K); magnetization studies of the Dy compounds show metamagnetic behavior with reorientation of spins at 6000 G. Band structure calculations indicate that the AlSi puckered hexagonal sheets in this structure are electronically distinct from the other surrounding structural motifs.