Simultaneous Optimization of Power Factor and Thermal Conductivity towards High-Performance InSb-Based Thermoelectric Materials

Thermoelectric performance of InSb is restricted by its low Seebeck coefficient and high thermal conductivity.Here,CuCl is employed to optimize simultaneously the electrical and thermal transport properties of InSb.The substitution of Cl for Sb results in enhanced electron effective mass,leading to high Seebeck coefficient of-159.9 μV/K and high power factor of 31.5 μW·cm~(-1)·K~(-2) at 733 K for InSb+5 wt% CuCl sample.In addition,CuCl doping creates hierarchical architectures composed of CugIn_4,Sb,Cu_2Sb in InSb,leading to a strengthened phonon scattering in a wide wavelength(i.e.,nano to meso scale),thus a low lattice thermal conductivity of 2.97 W·m~(-1)·K~(-1) at 733 K in InSb+5 wt% CuCl.As a result,a maximum ZT of 0.77 at 733 K has been achieved for the InSb+5 wt% CuCl sample,increasing by ～250% compared to pristine InSb.     

Zintl Phase BaAgSb: Low Thermal Conductivity and High Performance Thermoelectric Material in Ab Initio Calculation

Thermoelectric materials are critical parts in thermal electric devices.Here,Zintl phase BaAgSb in space group of P63/mmc is reported as a promising thermoelectric material in density function theory.The anisotropic lattice thermal conductivity and phonon transport properties are investigated in theory.The strong phonon-phonon scattering in BaAgSb exhibits ultra-low lattice thermal conductivity of 0.59 W·m~(-1)·K~(-1) along c-axis at 800 K,and high thermoelectric performance ZT=0.94 at 400 K.The mix of covalent and ionic bond supports high carrier mobility and low thermal conductivity.The unusual features make BaAgSb a potential thermoelectric material.     

Synthesis and thermoelectric properties of Nd-single filled p-type skutterudites

We report the synthesis of Nd-filled and Fe substituted p-type Ndx Fe_(3.2)Co_(0.8)Fe_(3.2)Co_(0.8)Sb_(12)(x=0.5,0.6,0.7,0.8,and 0.9)skutterudites by the solid-state reaction method.The influences of Nd filler on the electrical and thermal transport prop-erties are investigated in a temperature range from room temperature to 850 K.A lowest lattice thermal conductivity of 0.88 W·m~(-1)·K~(-1)is obtained in Nd0.8Fe_(3.2)Co_(0.8)Fe_(3.2)Co_(0.8)Sb_(12)at 673 K,which results from the localized vibration modes of fillers and the increase of grains boundaries.Meanwhile,the maximum power factor is 2.77 m W·m~(-1)·K~(-2)for the Nd_(0.9)Fe_(3.2)Co_(0.8)Fe_(3.2)Co_(0.8)Sb_(12)sample at 668 K.Overall,the highest dimensionless figure of merit z T=0.87 is achieved at 714 Kfor Nd_(0.9)Fe_(3.2)Co_(0.8)Fe_(3.2)Co_(0.8)Sb_(12).     

Phase transition and near-zero thermal expansion of Zr_(0.5)Hf_(0.5)VPO_7

The Zr_(0.5)Hf_(0.5)VPO_7 is successfully synthesized by the solid-state method with near-zero thermal expansion. Powder x-ray diffraction(XRD), Raman spectroscopy, thermal dilatometry, and scanning electron microscopy(SEM) are used to investigate the structure, the phase transition, and the coefficient of thermal expansion(CTE) of Zr_(0.5)Hf_(0.5)VPO_7. The investigation results show that the samples are of the single cubic type with a space group of Pa3ˉ at room temperature(RT).It can be inferred that the superstructure is transformed from the 3 × 3 × 3 superstructure to the 1 × 1 × 1 ideal crystal in a temperature range between 310 K and 323 K. The CTE is measured by a dilatometer to be 0.59 × 10~(-6) K~(-1)(310 K–673 K). The values of intrinsic(XRD) and extrinsic(dilatometric) thermal expansion are both near zero. The results show that Zr_(0.5)Hf_(0.5)VPO_7 has near-zero thermal expansion behavior over a wide temperature range.     

Enhancement of thermoelectric properties of SrTiO_3/LaNb–SrTiO_3 composite by different doping levels

Strontium titanate(STO)is an n-type oxide thermoelectric material,which has shown great prospects in recent years.The doping of La and Nb into STO can improve its power factor,whereas its thermal conductivity is still very high.Thus,in order to obtain a high thermoelectric figure-of-merit z T,it is very important to reduce its thermal conductivity.In this paper,using a combination of a hydrothermal method and a high-efficiency sintering method,we succeed in preparing a composite of pure STO and La Nb-doped STO,which simultaneously realizes lower thermal conductivity and higherSeebeck coefficient,therefore,the thermoelectric properties of STO are significantly improved.In the SrTiO_3/La Nb–SrTiO_3 bulk samples,the lowest thermal conductivity is 2.57 W·m~(-1)·K~(-1)and the highest z T is 0.35 at 1000 K for the STO/La_(10)Nb_(20)–STO sample.     

Thermal conductivity of carbon nanoring linked graphene sheets:A molecular dynamics investigation

Improving the thermal conduction across graphene sheets is of great importance for their applications in thermal management. In this paper, thermal transport across a hybrid structure formed by two graphene nanoribbons and carbon nanorings(CNRs) was investigated by molecular dynamics simulations. The effects of linker diameter, number, and height on thermal conductivity of the CNRs–graphene hybrid structures were studied respectively, and the CNRs were found effective in transmitting the phonon modes of GNRs. The hybrid structure with 2 linkers showed the highest thermal conductivity of 68.8 W·m~(-1)·K~(-1). Our work presents important insight into fundamental principles governing the thermal conduction across CNR junctions and provides useful guideline for designing CNR–graphene structure with superior thermal conductivity.     

Temperature-Dependent Galvanomagnetic Measurements on Doped InSb and InAs Grown by Liquid Encapsulated Czochralski

Resistivity, magnetoresistivity and Hall effect measurements in n-type Te-doped InSb and S-doped InAs samples grown by the liquid encapsulated Czochralski technique were carried out as a function of temperature (14-350K) and magnetic field (0-1.35 T). In Te-doped InSb, an impurity level with energy E1 = 3 meV and the activation energy E0 = 0.26 eV, which is the band gap energy, are obtained from the resistivity and Hall carrier concentration analysis. In S-doped InAs, both the linear and power law models are used in explaining the temperature-dependent resistivity. The effects of impurities on the electron and magnetic transportation properties of InAs and InSb have also been discussed.     

Thermal stability and electrical transport properties of Ge/Sn-codoped single crystalline β-Zn_4Sb_3 prepared by the Sn-flux method

This study prepares a group of single crystalline β-Zn_4Sb_3 with Ge and Sn codoped by the Sn-flux method according to the nominal stoichiometric ratios of Zn_(4.4)Sb_3 Ge_xSn_3(x = 0–0.15). The prepared samples possess a metallic luster surface with perfect appearance and large crystal sizes. The microscopic cracks or defects are invisible in the samples from the back-scattered electron image. Except for the heavily Ge-doped sample of x = 0.15, all the samples are single phase with space group R3c. The thermal analysis results show that the samples doped with Ge exhibit an excellent thermal stability.Compared with the polycrystalline Ge-substituted β-Zn_4Sb_3, the present single crystals have higher carrier mobility, and hence the electrical conductivity is improved, which reaches 7.48×10~4S·m~(-1) at room temperature for the x = 0.1 sample.The change of Ge and Sn contents does not improve the Seebeck coefficient significantly. Benefiting from the increased electrical conductivity, the sample with x = 0.075 gets the highest power factor of 1.45×10~(-3)W·m~(-1)·K~(-2) at 543 K.     

Thermoelectric properties of lower concentration K-doped Ca_3Co_4O_9 ceramics

The tuning of electron and phonon by ion doping is an effective method of improving the performances of thermoelectric materials. A series of lower concentration K-doped Ca_(3-x)K_xCo_4O_9(x = 0, 0.05, 0.10, 0.15) polycrystalline ceramic samples are prepared by combining citrate acid sol-gel method with cold-pressing sintering method. The single-phase compositions and plate-like grain morphologies of all samples are confirmed by x-ray diffraction and field emission scanning electron microscope. The effects of lower concentration K doping on the thermoelectric properties of the material are evaluated systematically at high temperatures(300–1026 K). Low concentration K doping causes electrical conductivity to increase up to 23% with little effect on the Seebeck coefficient. Simultaneously, the thermal conductivity of K-doped sample is lower than that of the undoped sample, and the total thermal conductivity reaches a minimum value of approximately1.30 W·m~(-1)·K~(-1), which may be suppressed mainly by the phonon thermal conduction confinement. The dimensionless figure-of-merit ZT of Ca_(2.95)K_(0.05)Co_4O_9 is close to 0.22 at 1026 K, representing an improvement of about 36% compared with that of Ca_3Co_4O_9, suggesting that lower concentration K-doped Ca_3Co_4O_9 series materials are promising thermoelectric oxides for high-temperature applications.     

First principle calculations of thermodynamic properties of pure graphene sheet and graphene sheets with Si,Ge,Fe,and Co impurities

The thermal properties of pure graphene and graphene–impurity(impurity = Fe,Co,Si,and Ge) sheets have been investigated at various pressures(0–7 GPa) and temperatures(0–900 K).Some basic thermodynamic quantities such as bulk modulus,coefficient of volume thermal expansion,heat capacities at constant pressure and constant volume of these sheets as a function of temperature and pressure are discussed.Furthermore,the effect of the impurity density and tensile strain on the thermodynamic properties of these sheets are investigated.All of these calculations are performed based on the density functional theory and full quasi harmonic approximation.     

Improvement of Thermoelectric Performance in BiCuSeO Oxide by Ho Doping and Band Modulation

We try to use Ho doping combined with band modulation to adjust the thermoelectric properties for BiCuSeO.The results show that Ho doping can increase the carrier concentration and increase the electrical conductivity in the whole temperature range.Although Seebeck coefficient decreases due to the increase of carrier concentration,it still keeps relatively high values,especially in the middle and high temperature range.On this basis,the band-modulation sample can maintain relatively higher carrier concentration while maintaining relatively higher mobility,and further improve the electrical transporting performance.In addition,due to the introduction of a large number of interfaces in the band-modulation samples,the phonon scattering is enhanced effectively and the lattice thermal conductivity is reduced.Finally,the maximal power factor(PF) of 5.18μW·cm~(-1)K~(-2) and the dimensionless thermoelectric figure of merits(ZT) of 0.81 are obtained from the 10% Ho modulation doped sample at 873 K.     

First-principles study of lattice dynamics and thermodynamics ofosmium under pressure

We have performed the first-principles linear response calculations of the lattice dynamics, thermal equation of state and thermodynamical properties of hcp Os metal by using the plane-wave pseudopotential method. The thermodynamical properties are deduced from the calculated Helmholtz free energy by taking into account the electronic contribution and lattice vibrational contribution. The phonon frequencies at Gamma point are consistent with experimental values and the dispersion curves at various pressures have been determined. The calculated volume, bulk modulus and their pressure derivatives as a function of temperature are in excellent agreement with the experimental results. The calculated specific heat indicates that the electronic contribution is important not only at very low temperatures but also at high temperatures due to the electronic thermal excitation. The calculated Debye temperature at a very low temperature is in good agreement with experimental values and drops to a constant until 100~K.     

High performance GaSb based digital-grown InGaSb/AlGaAsSb mid-infrared lasers and bars

InGaSb/AlGaAsSb double-quantum-well diode lasers emitting around 2 μm are demonstrated. The AlGaAsSb barriers of the lasers are grown with digital alloy techniques consisting of binary AlSb/AlAs/GaSb short-period pairs. Peak power conversion efficiency of 26% and an efficiency higher than 16% at 1 W are achieved at continuous-wave operation for a 2-mm-long and 100-μm-wide stripe laser. The maximum output power of a single emitter reaches to 1.4 W at 7 A.19-emitter bars with maximum efficiency higher than 20% and maximum power of 16 W are fabricated. Lasers with the short-period-pair barriers are proved to have improved temperature properties and wavelength stabilities. The characteristic temperature(T_0) is up to 140?C near room temperature(25–55?C).     

Properties of negative thermal expansion β-eucryptite ceramics prepared by spark plasma sintering

β-eucryptite powders are prepared by the sol-gel method through using tetraethoxysilane lithium nitrate and aluminum isopropoxide as starting materials. β-eucryptite ceramics are prepared by spark plasma sintering. The effects of sintering temperature on the negative thermal expansion properties of the β-eucryptite are investigated by x-ray diffraction(XRD), scanning electron microscopy, and thermal expansion test. The XRD results exhibit no change in the crystal structure of the sample prepared by different sintering processes. The negative thermal expansion properties increase with the increase of the sintering temperature. The coefficient of thermal expansion of β-eucryptite ceramics sintered at 1100℃ is calculated to be -4.93 × 10~(-6)℃~(-1). Crystallization behaviors of the ceramics may play an important role in the increase of negative thermal expansion of β-eucryptite. High sintering temperature could improve the crystallization behaviors of the ceramics and reduce the residue glass phase, which can improve the negative thermal expansion properties of β-eucryptite ceramics.     

Size-dependent thermal stresses in the core–shell nanoparticles

The thermal stress in a magnetic core–shell nanoparticle during a thermal process is an important parameter to be known and controlled in the magnetization process of the core–shell system. In this paper we analyze the stress that appears in a core–shell nanoparticle subjected to a cooling process. The external surface temperature of the system, considered in equilibrium at room temperature, is instantly reduced to a target temperature. The thermal evolution of the system in time and the induced stress are studied using an analytical model based on a time-dependent heat conduction equation and a differential displacement equation in the formalism of elastic displacements. The source of internal stress is the difference in contraction between core and shell materials due to the temperature change. The thermal stress decreases in time and is minimized when the system reaches the thermal equilibrium. The radial and azimuthal stress components depend on system geometry, material properties, and initial and final temperatures. The magnitude of the stress changes the magnetic state of the core–shell system. For some materials, the values of the thermal stresses are larger than their specific elastic limits and the materials begin to deform plastically in the cooling process. The presence of the induced anisotropy due to the plastic deformation modifies the magnetic domain structure and the magnetic behavior of the system.     

Magnetostructural transformation and magnetocaloric effect in Mn_(48-x)V_xNi_(42)Sn_(10) ferromagnetic shape memory alloys

In this work, we tuned the magnetostructural transformation and the coupled magnetocaloric properties of Mn_(48-x)V_xNi_(42)Sn_(10)(x = 0, 1, 2, and 3) ferromagnetic shape memory alloys prepared by means of partial replacement of Mn by V. It is observed that the martensitic transformation temperatures decrease with the increase of V content. The shift of the transition temperatures to lower temperatures driven by the applied field, the metamagnetic behavior, and the thermal hysteresis indicates the first-order nature for the magnetostructural transformation. The entropy changes with a magnetic field variation of 0–5 T are 15.2, 18.8, and 24.3 J·kg~(-1)·K~(-1) for the x = 0, 1, and 2 samples, respectively. The tunable martensitic transformation temperature, enhanced field driving capacity, and large entropy change suggest that Mn_(48-x)V_xNi_(42)Sn_(10) alloys have a potential for applications in magnetic cooling refrigeration.     

Sm–Co high-temperature permanent magnet materials

Permanent magnets capable of reliably operating at high temperatures up to ~450?C are required in advanced power systems for future aircrafts, vehicles, and ships. Those operating temperatures are far beyond the capability of Nd–Fe–B magnets. Possessing high Curie temperature, Sm–Co based magnets are still very important because of their hightemperature capability, excellent thermal stability, and better corrosion resistance. The extensive research performed around the year 2000 resulted in a new class of Sm_2(Co, Fe, Cu, Zr)_(17)-type magnets capable of operating at high temperatures up to 550?C. This paper gives a systematic review of the development of Sm–Co permanent magnets, from the crystal structures and phase diagrams to the intrinsic magnetic properties. An emphasis is placed on Sm_2(Co, Fe, Cu, Zr)_(17)-type magnets for operation at temperatures from 300?C to 550?C. The thermal stability issues, including instantaneous temperature coefficients of magnetic properties, are discussed in detail. The significance of nanograin structure, nanocrystalline, and nanocomposite Sm–Co magnet materials, and prospects of future rare-earth permanent magnets are also given.     

Thermodynamic behaviour of Rashba quantum dot in the presence of magnetic field

The thermodynamic properties of an In Sb quantum dot have been investigated in the presence of Rashba spin–orbit interaction and a static magnetic field. The energy spectrum and wave-functions for the system are obtained by solving the Schrodinger wave-equation analytically. These energy levels are employed to calculate the specific heat, entropy,magnetization and susceptibility of the quantum dot system using canonical formalism. It is observed that the system is susceptible to maximum heat absorption at a particular value of magnetic field which depends on the Rashba coupling parameter as well as the temperature. The variation of specific heat shows a Schottky-like anomaly in the low temperature limit and rapidly converges to the value of 2kB with the further increase in temperature. The entropy of the quantum dot is found to be inversely proportional to the magnetic field but has a direct variation with temperature. The substantial effect of Rashba spin–orbit interaction on the magnetic properties of quantum dot is observed at low values of magnetic field and temperature.     

Significant role of nanoscale Bi-rich phase in optimizing thermoelectric performance of Mg_3Sb_2

Mg_3Sb_(1.5)Bi_(0.5)-based alloys have received much attention, and current reports on this system mainly focus on the modulation of doping. However, there lacks the explanation for the choice of Mg_3Sb_(1.5)Bi_(0.5) as matrix. Here in this work,the thermoelectric properties of Mg_3Sb_(2-x)Bi_x(0.4 ≤ x ≤ 0.55) compounds are systematically investigated by using the first principles calculation combined with experiment. The calculated results show that the band gap decreases after Bi has been substituted for Sb site, which makes the thermal activation easier. The maximum figure of merit(ZT) is 0.27 at 773 K,which is attributed to the ultra-low thermal conductivity 0.53 W·m~(-1)·K~(-1) for x = 0.5. The large mass difference between Bi and Sb atoms, the lattice distortion induced by substituting Bi for Sb, and the nanoscale Bi-rich particles distributed on the matrix are responsible for the reduction of thermal conductivity. The introduction of Bi into Mg_3Sb_2-based materials plays a vital role in regulating the transport performance of thermoelectric materials.     

First-principles study of structural,electronic,elastic,and thermal properties of Imm2-BC

Using the first-principles method, we predict an orthorhombic boron–carbon binary structure with sp~ace group Imm2.This structure is verified to be dynamically and mechanically stable, and possesses a cavity of 27.5 ~2 that makes it a potential molecular sieve material. The C sp~2 and sp~3 hybridized bonding in Imm2 BC is an important factor for its structural stability. The energy band calculations reveal that Imm2 BC is a semiconductor with a band gap of 1.3 eV and has a promising application in the electro-optic field. The lattice thermal conductivity along the crystal [100] direction at room temperature is 186 W·m~(-1)·K~(-1), that is about 5 times higher than those along the [010] and [001] directions, which stems from the different group velocity along the crystal direction. Moreover, the acoustic-optical coupling is important for heat transp~ort in Imm2 BC, and the contribution of optical phonons to lattice thermal conductivity in the [100], [010], and [001]directions is 49%, 59%, and 61%, resp~ectively. This study gives a fundamental understanding of the structural, electronic,elastic, and heat transp~ort properties in Imm2 BC, further enriching the family of boron–carbon binary compounds.