Strong Anisotropic Thermal Conductivity in Polycrystalline Layers of (AgxSn1-xS)1.2(TiS2)2 with Prospects Toward Improved Thermoelectric Performance

Anisotropic tuning is of crucial importance for designing and developing high-performance thermoelectric materials. Here, a prominent anisotropic thermoelectric characteristic of Ag-substituted misfit-layered (SnS)_1.2(TiS₂)₂ alloys is investigated in the perpendicular (in-plane) and parallel (out-of-plane) to the pressing direction. In the in-plane direction, the (Ag_xSn_1-xS)_1.2(TiS₂)₂ alloys possess a highest power factor of 0.86 mW K⁻² m⁻¹ at 520 K, while in the out-of-plane direction the lowest lattice thermal conductivity (0.37 W K⁻¹ m⁻¹) is achieved, which is driven by the natural intercalated structure where the out-of-plane phonon is strongly scattered without affecting the in-plane mobility. Moreover, along the in-plane orientation, the introduced point defects due to the substitution of Sn by Ag trigger a significant reduction of lattice thermal conductivity. In contrast, along the out-of-plane orientation, the decreased carrier concentration enables a large Seebeck coefficient and power factor, ultimately ensuring high thermoelectric performance. The present finding in the misfit-layered chalcogenide opens up a new route to manipulating thermoelectrics via anisotropy engineering.     

Thermoelectric performance in pseudo-ternary (PbTe)0.95-x(Sb2Se3)x(PbS)0.05 system with ultra-low thermal conductivity via multi-scale phonon scattering

Among the intermediate temperature (500–900 K) thermoelectric materials, both the p- and n-type lead telluride (PbTe) compounds have attracted extensive interests. Till date various approaches were adopted to enhance the thermoelectric performance of n-type PbTe-based materials as they show greater potential space for further improvement compared to p-type ones. Herein, a pseudo-ternary n-type (PbTe)_0.95-x(Sb₂Se₃)_x(PbS)_0.05 system was designed and a large value of ZT = 1.61 at 850 K in case of x = 0.01 was achieved. Two factors are responsible for the improved thermoelectric performance. The incorporation of lead sulfide is the key factor to maintain a high level of power factor above 700 K and the multi-scale hierarchical architectures yield ultra-low thermal conductivity.     

Effect of Ge4+ and Mg2+ doping on superconductivity,fluctuation induced conductivity and interplanar coupling of TlSr2CaCu2O7−δ superconductors

Substitution of Ge⁴⁺ in place of Cu in Tl_0.85Cr_0.15Sr₂CaCu_2?xGe_xO_7?δ (x = 0–0.6) showed initial increase in zero critical temperature value, T_{c zero} from 98 K (x = 0) to 100 K (x = 0.1) and in the range of 85–86 K for x = 0.2–0.3. The slow decrease in T_{c zero} is unexpected as tetravalent Ge⁴⁺ substitution is expected to strongly reduce hole concentration in the samples and suppress T_{c zero}. Excess conductivity analyses of resistance versus temperature data based on Asmalazov–Larkin (AL) theory revealed that the substitution induced 2D-to-3D transition of fluctuation induced conductivity with the highest transition temperature, T_2D–3D observed at x = 0.1. FTIR spectroscopy analysis indicates Ge⁴⁺ substitution cause reduction in CuO₂/GeO₂ interplanar distance while our calculation based on Lawrence–Doniach model revealed highest superconducting coherence length, ξ_c(0) and interplanar coupling, J at x = 0.3. On the other hand, substitution of divalent Mg²⁺ for Ca²⁺ in (Tl_0.5Pb_0.5)(Sr_1.8Yb_0.2)(Ca_1?yMg_y)Cu₂O₇ (y = 0–1.0), which is not expected to directly vary hole concentration, surprisingly caused T_{c zero} to increase from 89.6 K (y = 0) to an optimum value of 95.9 K (y = 0.6) before decreasing with further increase in y. Excess conductivity analyses showed 2D-to-3D transition of fluctuation induced conductivity for all samples where the highest T_2D–3D was at y = 0.4. Similar calculation revealed highest values of ξ_c(0) and J also at y = 0.4. FTIR analysis of the samples indicates inequivalent Cu(1)O(2)Pb/Tl lengths and possible tilting of CuO₂ plane as a result of Mg²⁺ substitution. The increased ξ_c(0) and J as a result of the Ge⁴⁺ and Mg²⁺ substitutions are suggested to contributed to sustenance of superconductivity above 80 K in the samples.     

Structural,vibrational study and superprotonic behavior of a new mixed dipotassium hydrogenselenate dihydrogenphosphate K2(HSeO4)1.5(H2PO4)0.5

Ongoing studies of the KHSeO₄–KH₂PO₄ system aiming at developing novel proton conducting solids resulted in the new compound K₂(HSeO₄)_1.5(H₂PO₄)_0.5 (dipotassium hydrogenselenate dihydrogenphosphate). The crystals were prepared by a slow evaporation of an aqueous solution at room temperature. The structural properties of the crystals were characterized by single-crystal X-ray analysis: K₂(HSeO₄)_1.5(H₂PO₄)_0.5 (denoted KHSeP) crystallizes in the space group P 1¯ with the lattice parameters: a = 7.417(3) Å, b = 7.668(2) Å, c = 7.744(5) Å, α = 71.59(3)°, β = 87.71(4)° and γ = 86.04(6)°. This structure is characterized by HSeO₄⁻ and disordered (H_xSe/P)O₄⁻ tetrahedra connected to dimers via hydrogen bridges. These dimers are linked and stabilized by additional hydrogen bonds (O–H–O) and hydrogen bridges (O–H…O) to build chains of dimers which are parallel to the [0, 1, 0] direction at the position x = 0.5.The differential scanning calorimetry diagram showed two anomalies at 493 and 563 K. These transitions were also characterized by optical birefringence, impedance and modulus spectroscopy techniques. The conductivity relaxation parameters of the proton conductors in this compound were determined in a wide temperature range. The transport properties in this material are assumed to be due to H⁺ protons hopping mechanism.     

Functional derivative of Tc with α2(ω)F(ω) for an anisotropic superconductor

The functional derivative δT_c/δα²(ω)F(ω) of the critical temperature (T_c) with the electron-phonon spectral density (α²(ω)F(ω)) gives information on the effectiveness of various phonon modes in enhancing T_c. For an anisotropic superconductor, it is found that δT_c/δα²(ω)F(ω) goes negative at some small but finite phonon energy. This contrasts with the isotropic case for which it is well known that the functional derivative is positive everywhere. Thus, very low energy phonons reduce T_c in an anisotropic superconductor which is similar to the known effects of static impurities that wash out anisotropy and hence reduce T_c.     

Negative c-axis magnetoresistance in graphite

We have studied the c-axis interlayer magnetoresistance (ILMR), Rc(B) in graphite. The measurements have been performed on strongly anisotropic highly oriented pyrolytic graphite (HOPG) and single crystalline Kish graphite samples in magnetic field up to B=9 T, and the temperature interval 2 K?T?300 K. We have observed negative magnetoresistance, dRc/dB<0, for B‖c-axis for both samples above a certain field Bm(T)>5.4 T and 0.2 T for HOPG and Kish graphite, respectively. The results can be understood consistently by assuming that ILMR is related to a tunneling between zero-energy Landau levels of quasi-two-dimensional Dirac fermions, in a close analogy with the behavior reported for α-(BEDT-TTF)₂I₃ [N. Tajima, et al., Phys. Rev. Lett. 102 (2009) 176403], another multilayer Dirac electron system.     

Inelastic neutron scattering on iron-based superconductor BaFe2(As,P)2

Inelastic neutron scattering has been performed on powder sample of an iron-based superconductor BaFe₂(As_0.65P_0.35)₂ with superconducting transition temperature (T_c) = 30 K, whose superconducting (SC) order parameter is expected to have line node. In the normal state, constant-E scan of dynamical structure factor, S(Q, E), exhibits a peak structure centered at momentum transfer Q ～ 1.20 Å^?1, corresponding to antiferromagnetic wave vector. Below T_c, the redistribution of the magnetic spectral weight takes place, resulting in the formation of a peak at E ～ 12 meV and a gap below 6 meV. The enhanced magnetic peak structure is ascribed to the spin resonance mode, evidencing sign change in the SC order parameter similar to other iron-based high-T_c superconductors. It suggests that fully-gapped s_± symmetry dominates in this superconductor, which gives rise to high-T_c (=30 K) despite the nodal symmetry.     

Superconducting transition parameters in aluminum-lithium alloys (0-10 at.% Li)

The superconducting transition temperatures T_c of face-centered cubic Al_1−x-Li_x alloys (x=0-0.10) exhibit a minimum near x=0.03 (3 at.% Li). The McMillan strong-coupling T_c equation yields a similar trend of the electron-phonon coupling constant λ. Meanwhile, the density of states at the Fermi level N(0) decreases monotonically with increasing x. It appears that T_c drops initially due to a reduced N(0), which is then overtaken by alloying-enhanced factors of phonon or electron-phonon interaction.     

Magnetic properties of uranium hexacyanomanganate

A Prussian blue type compound of the stoichiometric composition U^IV[Mn^II(CN)₆]·5H₂O has been prepared. It has been shown that the compound exhibits ferrimagnetism with a Curie temperature T_c=36.8 K.     

Low field AC susceptibility study of intergranular critical current density in Mg-substituted CuBa2Ca3Cu4O12−y high temperature superconductors

Measurements of the a.c.susceptibility (χ=χ′+iχ″) have been made on the Mg substituted high T_C superconducting system, CuBa₂(Mg_xCa_1−x)₃Cu₄O_12−y (Cu-1234) with x=0, 0.10 & 0.20, at different values of the a.c.field amplitude. Estimates of the intergranular critical current density(J_C) made from the field dependent χ″-T curves show an improvement in the Mg-substituted Cu-1234 system. Results have been analysed in the light of the crystal structure and the superconducting anisotropy factor (γ=ξ_ab/ξ_c) of the Cu-1234 system. Lower superconducting anisotropy emanating from Mg substitution has been found to be significant, resulting in better superconducting properties.     

Electrical,magnetic and magnetocaloric properties of polycrystalline Pr0.63A0.07Sr0.3MnO3 (A=Pr,Sm and Bi)

We studied the effects of the partial substitution (10%) of praseodymium by samarium and bismuth, on the structural, magnetic, magnetocaloric and electrical properties of the Pr_0.63A_0.07Sr_0.3MnO₃ (A=Pr, Sm and Bi) manganites prepared using the solid state reaction. Refinement of the X-ray diffraction patterns shows that all our samples are single phase and crystallize in the orthorhombic structure with Pnma space group. Magnetic studies indicate that all the samples exhibit a ferromagnetic–paramagnetic transition with increasing temperature. Curie temperature T_C decreases by substitution. M(H) curves indicate the presence of some antiferromagnetic domains in the substituted samples testifying the phase-separated nature of these samples. The magnetic entropy curves –ΔS(T) show a maximum in vicinity of T_C. Important values of maximum of −ΔS are recorded for our compounds. For the parent compound, we found 4.59 J/kg K for an applied magnetic field of 2 T at T_C=266 K which raises the possibility of using this compound as a magnetic refrigerant. The temperature dependence of the electrical resistivity ρ(T) indicates that all compounds exhibit a metal-insulator transition with increasing temperature. Electrical study suggests the presence of a correlation between electrical and magnetic properties.     

Dielectric properties and study of AC electrical conduction mechanisms by non-overlapping small polaron tunneling model in Bis(4-acetylanilinium) tetrachlorocuprate(II) compound

In the present work, the synthesis and characterization of the Bis(4-acetylanilinium) tetrachlorocuprate(II) compound are presented. The structure of this compound is analyzed by X-ray diffraction which confirms the formation of single phase and is in good agreement the literature. Indeed, the Thermo gravimetric Analysis (TGA) shows that the decomposition of the compound is observed in the range of 420–520 K. However, the differential thermal analysis (DTA) indicates the presence of a phase transition at T=363 k. Furthermore, the dielectric properties and AC conductivity were studied over a temperature range (338–413 K) and frequency range (200 Hz–5 MHz) using complex impedance spectroscopy. Dielectric measurements confirmed such thermal analyses by exhibiting the presence of an anomaly in the temperature range of 358–373 K. The complex impedance plots are analyzed by an electrical equivalent circuit consisting of resistance, constant phase element (CPE) and capacitance. The activation energy values of two distinct regions are obtained from log σT vs 1000/T plot and are found to be E=1.27 eV (T<363 K) and E=1.09 eV (363 K<T).The frequency dependence of ac conductivity, σ_ac, has been analyzed by Jonscher's universal power law σ(ω)=σ_dc+Aω^s. The value of s is to be temperature-dependent, which has a tendency to increase with temperature and the non-overlapping small polaron tunneling (NSPT) model is the most applicable conduction mechanism in the title compound.     

Magnetic and electrical properties of bismuth cobaltite Bi24(CoBi)O40 with charge ordering

The compound Bi₂₄(CoBi)O₄₀ has been synthesized using the solid-phase reaction method. The temperature and field dependences of the magnetic moment in the temperature range 4 K < T < 300 K and the temperature dependences of the EPR line width and g-factor at temperatures 80 K < T < 300 K have been investigated. The electrical resistivity and thermoelectric power have been measured in the temperature range 100 K < T < 1000 K. The activation energy has been determined and the crossover of the thermoelectric power from the phonon mechanism to the electron mechanism with variations in the temperature has been observed. The thermal expansion coefficient of the samples has been measured in the temperature range 300 K < T < 1000 K and the qualitative agreement with the temperature behavior of the electrical resistivity has been achieved. The electrical and structural properties of the compound have been explained in the framework of the model of the electronic-structure transition with inclusion of the exchange and Coulomb interactions between electrons and the electron-phonon interaction.     

Improved calculation of the structure functions of the nucleon in the O(4, 2)-infinite multiplet model

A new investigation of the inelastic electon scattering from proton in the O(4, 2) models is presented. The resultant explicit structure functions in the limit satisfy scaling, F₁(ξ) ≠ 0 (σ_T ≠ 0), the Drell-Yan relation F₂(ξ) ～ (1?ξ)³ and, approximately, the Callan-Gross relation F₂(ξ) ≈ 2ξF₁(ξ).     

Low-temperature x-ray diffraction studies of the crystallographic parameters and thermal expansion of (CH3)2NH2Al(SO4)2 · 6H2O crystals

The a, b, c, and β crystallographic parameters of the (CH₃)₂NH₂Al(SO₄)₂ · 6H₂O crystal (DMAAS) have been measured by x-ray diffraction in the 90–300-K temperature range. The thermal expansion coefficients along the principal crystallographic axes α_a, α_b, and α_c have been determined. It was shown that, as the temperature is increased, the parameter α decreases and b increases, whereas c decreases for T<T _c (where T _c is the transition temperature) and increases for T>T _c, so that one observes a minimum in the c=f(T) curve in the region of the phase transition (PT) temperature T _c ～ 152 K. The thermal expansion coefficients α_a, α_b, and α_c vary in a complicated manner with increasing temperature, more specifically, α_a and α_c assume negative values at low temperatures, and the α_a=f(T), α_b=f(T), and α_c=f(T) curves exhibit anomalies at the PT point. The crystal has been found to be substantially anisotropic in thermal expansion.     

Charge density wave transport in (TaSe4)2I

We report non linear transport properties below the metal-insulat transition temperature T_° = 263 K in the halogened metal transition tetrachalcogenide (TaSe₄)₂I. These non linear properties are similar to those of NbSe₃ and TaS₃ and indicate that (TaSe₄)₂I is a new compound exhibiting charge density wave transport.     

Superconductivity and thermal properties of sulphur doped FeTe with effect of oxygen post annealing

Here, we report the synthesis and characterization of sulphur-substituted iron telluride i.e. FeTe_1?xS_x; (x = 0–30 %) system and study the impact of low temperature oxygen (O₂) annealing as well. Rietveld analysis of room temperature X-ray diffraction (XRD) patterns shows that all the compounds are crystallized in a tetragonal structure (space group P4/nmm) and no secondary phases are observed. Lattice constants are decreased with increasing S concentration. The parent compound of the system i.e. FeTe does not exhibit superconductivity but shows an anomaly in the resistivity measurement at around 78 K, which corresponds to a structural phase transition. Heat capacity C_p(T) measurement also confirms the structural phase transition of FeTe compound. Superconductivity appears by S substitution; the onset of superconducting transition temperature is about 8 K for FeTe_0.75S_0.25 sample. Thermoelectric power measurements S(T) also shows the superconducting transition at around 7 K for FeTe_0.75S_0.25 sample. The upper critical fields H_c2(10%), H_c2(50%) and H_c2(90%) are estimated to be 400, 650 and 900 kOe respectively at 0 K by applying Ginzburg Landau (GL) equation. Interestingly, superconducting volume fraction is increased with low temperature (200 °C) O₂ annealing at normal pressure. Detailed investigations related to structural (XRD), transport [S(T), R(T)H], magnetization (AC and DC susceptibility) and thermal [C_p(T)] measurements for FeTe_1?xS:O₂ system are presented and discussed.     

Spin glass behavior and critical analysis across the magnetic phase transition in Gd2CoMnO6: dc magnetization and ac susceptibility study

We report here on critical analysis across magnetic phase transition and spin dynamics in Gd₂CoMnO₆. We found that this material behaves differently below and above the applied magnetic field of 20 kOe. The magnetic phase transition switches from nearly mean-field type to unusual class and T_c shifts towards the high temperature above 20 kOe field. The nature of the magnetic phase transition is explored by carrying out critical analysis at low as well as at high magnetic field. The critical exponents obtained at low field using Kouvel-Fisher method are β = 0.65 (2) γ = 0.90 (2), δ = 2.43 and T_c = 120 K. Apparently, these values of critical exponents appear close to mean-field model. For high field the critical exponents are β = 1.24 (2) γ = 0.64 (5), δ = 1.51 (3) and T_c = 128 K. The critical exponents show significant deviation from any universal class. This switchover in the nature of the magnetic phase transition is unique and not seen in many compounds. The formation of non-Griffiths-like clusters in this compound can be a reason for such unique behavior. Further, ac susceptibility has been measured to understand the spin dynamics in detail. The dispersion of frequency-dependent χ_ac below T_c confirms a spin glass state in this material. The observed value of τ_o and T_o indicate the slow dynamic spin which is caused by co-existence of Co/Mn spin magnetic moments. The magneto-caloric effect is also presented for Gd₂CoMnO₆ in this study. The magnetic study and critical analysis across the phase transition reveal a switchover in the nature of phase transition in this material. A non-Griffiths like cluster formation above T_c is found and dynamic susceptibility study reveals a spin glass state below T_c in Gd₂CoMnO₆.     

Physical property characterization of bulk MgB<Subscript>2</Subscript> superconductor

We report synthesis, structure/micro-structure, resistivity under magnetic field [ρ(T)H], Raman spectra, thermoelectric power S(T), thermal conductivity κ(T), and magnetization of ambient pressure argon annealed polycrystalline bulk samples of MgB₂, processed under identical conditions. The compound crystallizes in hexagonal structure with space group P6/mmm. Transmission electron microscopy (TEM) reveals electron micrographs showing various types of defect features along with the presence of 3–4 nm thick amorphous layers forming the grain boundaries of otherwise crystalline MgB₂. Raman spectra of the compound at room temperature exhibited characteristic phonon peak at 600 cm^-1. Superconductivity is observed at 37.2 K by magnetic susceptibility χ(T), resistivity ρ(T), thermoelectric power S(T), and thermal conductivity κ(T) measurements. The power law fitting of ρ(T) give rise to Debye temperature (Θ_D) at 1400 K which is found consistent with the theoretical fitting of S(T), exhibiting Θ _D of 1410 K and carrier density of 3.81 × 10²⁸/m³. Thermal conductivity κ(T) shows a jump at 38 K, i.e., at T_c, which was missing in some earlier reports. Critical current density (J_c) of up to 10⁵ A/cm² in 1–2 T (Tesla) fields at temperatures (T) of up to 10 K is seen from magnetization measurements. The irreversibility field, defined as the field related to merging of M(H) loops is found to be 78, 68 and 42 kOe at 4, 10 and 20 K respectively. The superconducting performance parameters viz. irreversibility field (H_irr) and critical current density J_c(H) of the studied MgB₂ are improved profoundly with addition of nano-SiC and nano-diamond. The physical property parameters measured for polycrystalline MgB₂ are compared with earlier reports and a consolidated insight of various physical properties is presented.     

BaT2As2 single crystals (T = Fe,Co, Ni) and superconductivity upon Co-doping

The crystal structure and physical properties of BaFe₂As₂, BaCo₂As₂, and BaNi₂As₂ single crystals are surveyed. BaFe₂As₂ gives a magnetic and structural transition at T_N = 132(1) K, BaCo₂As₂ is a paramagnetic metal, while BaNi₂As₂ has a structural phase transition at T₀ = 131 K, followed by superconductivity below T_c = 0.69 K. The bulk superconductivity in Co-doped BaFe₂As₂ below T_c = 22 K is demonstrated by resistivity, magnetic susceptibility, and specific heat data. In contrast to the cuprates, the Fe-based system appears to tolerate considerable disorder in the transition metal layers. First principles calculations for BaFe_1.84Co_0.16As₂ indicate the inter-band scattering due to Co is weak.