Effects of Rattling Behavior of K and Cd Atoms along Different Directions in Anisotropic KCdAs on Lattice Thermal Transport and Thermoelectric Properties

We employ advanced first principles methodology,merging self-consistent phonon theory and the Boltzmann transport equation,to comprehensively explore the thermal transport and thermoelectric properties of KCdAs.Notably,the study accounts for the impact of quartic anharmonicity on phonon group velocities in the pursuit of lattice thermal conductivity and investigates 3ph and 4ph scattering processes on phonon lifetimes.Through various methodologies,including examining atomic vibrational modes and analyzing 3ph and 4ph scattering processes,the article unveils microphysical mechanisms contributing to the lowκL within KCdAs.Key features include significant anisotropy in Cd atoms,pronounced anharmonicity in K atoms,and relative vibrations in non-equivalent As atomic layers.Cd atoms,situated between As layers,exhibit rattling modes and strong lattice anharmonicity,contributing to the observed lowκL.Remarkably flat bands near the valence band maximum translate into high PF,aligning with ultralowκL for exceptional thermoelectric performance.Under optimal temperature and carrier concentration doping,outstanding ZT values are achieved:4.25(a(b)-axis,p-type,3×10^(19)cm^(−3),500 K),0.90(c-axis,p-type,5×10^(20)cm^(−3),700 K),1.61(a(b)-axis,n-type,2×10^(18)cm^(−3),700 K),and 3.06(c-axis,n-type,9×10^(17)cm^(−3),700 K).

Phase transition and high temperature thermoelectric properties of copper selenide Cu_(2-x) Se (0 ≤ x ≤ 0.25)

With good electrical properties and an inherently complex crystal structure, Cu2-xSe is a potential ＂phonon glass electron crystal＂ thermoelectric material that has previously not attracted much interest. In this study, Cu2-xSe （0 ≤ x ≤0.25） compounds were synthesized by a melting-quenching method, and then sintered by spark plasma sintering to obtain bulk material. The effect of Cu content on the phase transition and thermoelectric properties of Cu2-xSe were investigated in the temperature range of 300 K-750 K. The results of X-ray diffraction at room temperature show that Cu2-xSe compounds possess a cubic structure with a space group of Fm3m （#225） when 0.15 〈 x ≤ 0.25, whereas they adopt a composite of monoclinic and cubic phases when 0 ≤x ≤ 0.15. The thermoelectric property measurements show that with increasing Cu content, the electrical conductivity decreases, the Seebeck coefficient increases and the thermal conductivity decreases. Due to the relatively good power factor and low thermal conductivity, the nearly stoichiometric Cu2Se compound achieves the highest ZT of 0.38 at 750 K. It is expected that the thermoelectric performance can be further optimized by doping appropriate elements and/or via a nanostructuring approach.

Effects of nano-TiO_2 dispersion on thermoelectric properties of Co_4Sb_(11.7)Te_(0.3) composites

Nano-TiO2/Co4Sb11.7Te0.3 composites were prepared by mechanical alloying (MA) and cold isostatic pressing (CIP) process.The phase composition,microstructure,and thermoelectric properties were characterized.The diffraction spectra of all samples well corresponds to CoSb3 skutterudite diffraction plane.TiO2 agglomerates into irregular clusters.They locate at the grain boundaries or some are distributed on the surface of Co4Sb11.7Te0.3 particles.For composites with high TiO2 content (0.6% and 1.0% TiO2),the phonon scattering by TiO2 particle,pores,and small size grains can result in a remarkable reduction in thermal conductivity.The maximum value of ZT is 0.79 for sample with 0.6 wt.% TiO2 at 700 K,which is 11% higher than that of non-dispersed sample.

Effect of erbium substitution on thermoelectric properties of complex oxide Ca_3Co_2O_6 at high temperatures

Polycrystalline particles of Ca3-xErxCo2O6 （x=0.0, 0.15, 0.3, 0.45 and 0.6） were synthesized using sol-gel method combined with Low Temperature Sintering procedure （LTS） to evaluate the effect of Er substitution on the thermoelectric properties of Ca3Co2O6. The crystal structure and microstructure were investigated using X-ray diffraction, infrared spectroscopy and scanning electron microscope. The electrical conductivity and Seebeck coefficient of the complex oxides were measured from 300 to 1073 K. The results showed that all the sampies were p-type semiconductors. The electrical conductivity increased with the increase in temperature. Er substitutions at Ca site affected carrier concentrations and carder mobility, resulting an increase in Seebeck coefficient and decrease in electrical conductivity. The power factor of Ca2.85Er0.15Co2O6 reached 10.66 μw/mK^2 at 1073 K.

Graphene-enhanced thermoelectric properties of p-type skutterudites

Nanocomposite is proved to be an effective method to improve thermoelectric performance.In the present study,graphene is introduced into p-type skutterudite La0.8Ti0.1Ga0.1Fe3CoSb12 by plasma-enhanced chemical vapor deposition（PECVD）method to form skutterudite/graphene nanocomposites.It is demonstrated that the graphene has no obvious effect on the electrical conductivity of La0.8Ti0.1Ga0.1Fe3CoSb12,but the Seebeck coefficient is slightly improved at high temperature,thereby leading to high power factor.Furthermore,due to the enhancement of phonon scattering by the graphene,the lattice thermal conductivity is reduced significantly.Ultimately,the maximum z T value of La0.8Ti0.1Ga0.1Fe3CoSb12/graphene is higher than that of graphene-free alloy and reaches to 1.0 at 723 K.Such an approach raised by us enriches prospects for future practical application.

Enhanced thermoelectric properties of p-type polycrystalline SnSe by regulating the anisotropic crystal growth and Sn vacancy

Thermoelectric selenides have attracted more and more attentions recently.Herein,p-type Sn Se polycrystalline bulk materials with good thermoelectric properties are presented.By using the SnSe2 nanostructures synthesized via a wetchemistry route as the precursor,polycrystalline Sn Se bulk materials were successfully obtained by a combined heattreating process under reducing atmosphere and following spark plasma sintering procedure.As a reference,the Sn Se nanostructures synthesized via a wet-chemistry route were also fabricated into polycrystalline bulk materials through the same process.The thermoelectric properties of the Sn Se polycrystalline transformed from SnSe2 nanostructures indicate that the increasing of heattreating temperature could effectively decrease the electrical resistivity,whereas the decrease in Seebeck coefficient is nearly invisible.As a result,the maximum power factor is enhanced from 5.06×10^-4W/m·K^2 to 8.08×10^-4W/m·K^2 at 612℃.On the other hand,the reference sample,which was obtained by using Sn Se nanostructures as the precursor,displays very poor power factor of only 1.30×10^-4W/m·K^2 at 537℃.The x-ray diffraction（XRD）,scanning electron microscope（SEM）,x-ray fluorescence（XRF）,and Hall effect characterizations suggest that the anisotropic crystal growth and existing Sn vacancy might be responsible for the enhanced electrical transport in the polycrystalline Sn Se prepared by using SnSe2 precursor.On the other hand,the impact of heat-treating temperature on thermal conductivity is not obvious.Owing to the boosting of power factor,a high z T value of 1.07 at 612℃ is achieved.This study provides a new method to synthesize polycrystalline Sn Se and pave a way to improve the thermoelectric properties of polycrystalline bulk materials with similar layered structure.

The First Principles Investigations of the Thermoelectric Properties of GaN with p-and n-Type Doping

We investigate the thermoelectric properties of GaN with p- and n-type doping by the first principles calculation and the semi-classical Boltzmann theory. We find that the power factors （Sacr） of p-type GaN （-3500 μW/mK2） is about twice that of the n-type （-1750 μW/mK2）, which indicates the thermoelectric properties of p-type GaN would be better. Thermal conductivity of GaN crystal decreases rapidly as the temperature increases, but it is still too large for thermoelectric applications. The figure of merit （ZT） estimated at 1500 K is 0.134 for p-type GaN crystal and 0.062 for the n-type.

High temperature thermoelectric properties of highly c-axis oriented Bi_2Sr_2Co_2O_y thin films fabricated by pulsed laser deposition

High-temperature thermoelectric transport property measurements have been performed on the highly c-axis oriented Bi2Sr2Co20v thin films prepared by pulsed laser deposition on LaA1Oa （001）. Both the electric resistivity p and the seebeck coefficient S of the film exhibit an increasing trend with the temperature from 300 K-1000 K and reach up to 4.8 m. cm and 202 V/K at 980 K, resulting in a power factor of 0.85 mW/mK which are comparable to those of the single crystalline samples. A small polaron hopping conduction can be responsible for the conduction mechanism of the film at high temperature. The results demonstrate that the Bi2Sr2Co2Oy thin film has potential application has high temperature thin film thermoelectric devices,

Enhanced thermoelectric properties of Co_(1-x-y)Ni_(x+y)Sb_(3-x)Sn_x materials

Co1-x-yNix＋ySb3-xSnx polycrystals were fabricated by vacuum melting combined with hot-press sintering. The effect of alloying on the thermoelectric properties of unfilled skutterudite CO1-xNixSb3-xSnx was investigated. A leap of electrical conductivity from the Co0.93Ni0.07Sb2.93Sn0.07 sample to the Co0.88Ni0.12Sb288Sn0.12 sample occurs during the measurement of electrical conductivity, indicating the adjustment of band structure by proper alloying. The results show that alloying enhances the power factor of the materials. On the basis of alloying, the thermoelectric properties of Coo.88Nio.12Sb2.ssSno.12 are improved by Ni-doping. The thermal conductivities of Ni-doping samples have no reduction, but their power factors have obvious enhancement. The power factor of Co0.81Ni0.09Sb2.88Sn0.12 reaches 3.0 mW-m-1·K-2 by Ni doping. The dimensionless thermoelectric figure of merit reaches 0.55 at 773 K for the unfilled Co0.81Ni0.19 Sb2.88Sn0.12,

Solvothermal synthesis and thermoelectric properties of skutterudite compound Fe_(0.25)Ni_(0.25)Co_(0.5)Sb_3

Nanostructured skutterudite-related compound Fe0.25Ni0.25Co0.5Sb3 was synthesized by a solvothermal method using FeCl3, NiCl2, CoCl2, and SbCl3 as the precursors and NaBH4 as the reductant. The solvothermally synthesized powders consisted of fine granules with an average particle size of tens of nanometers. The bulk material was prepared by hot pressing the powders. Transport property measurements indicated a heavily doped semiconductor behavior with n-type conduction. The thermal conductivity is about 1.83 W·m-1·K-1 at room temperature and decreases to 1.57 W·m-1·K-1 at 673 K. The low thermal conductivity is attributed to small grain size and high porosity. A maximum dimensionless figure of merit of 0.15 is obtained at 673 K.

Optoelectronic and thermoelectric properties of Zintl YLi_(3)A_(2)(A = Sb,Bi) compounds through modified Becke-Johnson potential

In the present work,we investigate the structural,optoelectronic and thermoelectric properties of the YLi3X2(X = Sb,Bi) compounds using the full potential augmented plane wave plus local orbital(FP-APW+lo) method.The exchangecorrelation potential is treated with the generalized gradient approximation/local density approximation(GGA/LDA) and with the modified Becke-Johnson potential(TB-mBJ) in order to improve the electronic band structure calculations.In addition,the estimated ground state properties such as the lattice constants,external parameters,and bulk moduli agree well with the available experimental data.Our band structure calculations with GGA and LDA predict that both compounds have semimetallic behaviors.However,the band structure calculations with the GGA/TB-mBJ approximation indicate that the ground state of the YLi3Sb2compound is semiconducting and has an estimated indirect band gap(Γ-L) of about 0.036 eV while the ground state of YLi3Bi2compound is semimetallic.Conversely the LDA/TB-mBJ calculations indicate that both compounds exhibit semiconducting characters and have an indirect band gap(Γ-L) of about 0.15 eV and 0.081 eV for YLi3Sb and YLi3Bi2respectively.Additionally,the optical properties reveal strong responses of the herein materials in the energy range between the IR and extreme UV regions.Thermoelectric properties such as thermal conductivity,electrical conductivity,Seebeck coefficient,and thermo power factors are also calculated.

Crystal Structures and Thermoelectric Properties of Sm-Filled Skutterudite Compounds Sm_yFe_xCo_(4-x)Sb_(12)

Polycrystalline samples of Sm partially filled skutterudites SmyFexCo4-xSb12 were prepared by melting and Spark Plasma Sintering technique. The results of Rietveld refinement showed that the obtained SmyFexCo4-xSb12 samples possessed filled skutterudite structures. The thermal parameter （B） of Sm is larger than that of Sb, Fe, and Co, indicating that Sm ＂rattled＂ in Sb-icosahedron voids. The effects of filling atom Sm on thermoelectric properties of these compounds were investigated. With the increase of Sm filling fraction （y）, electrical conductivity decreased, Seebeck coefficient increased and had a maximum value when y was 0.38; thermal conductivity reduced and had a minimum value when y was 0. 32. At 750 K, the highest figure of merit of 0.68 was obtained for Sm0.32Fe1.47Co2.53Sb12.

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.

Preparation and Thermoelectric Properties of SiO_2/β-Zn_4Sb_3 Nanocomposite Materials

A series of SiO2/β-Zn4Sb3 core-shell composite particles with 3, 6, 9, and 12 nm of SiO2 shell in thickness were prepared by coatingβ-Zn4Sb3 microparticles with SiO2 nanoparticles formed by hydrolyzing the tetraethoxysilane in alcohol-alkali-water solution. SiO2/β-Zn4Sb3 nanocomposite thermoelectric materials were fabricated with these core-shell composite particles by spark plasma sintering （SPS） method. Microstructure, phase composition, and thermoelectric properties of SiO2/β-Zn4Sb3 nanocomposite thermoelectric materials were systemically investigated. The results show thatβ-Zn4Sb3 microparticles are uniformly coated by SiO2 nanoparticles, and no any phase transformation reaction takes place during SPS process. The electrical and thermal conductivity gradually decreases, and the Seebeck coefficient increases compared to that ofβ-Zn4Sb3 bulk material, but the increment of Seebeck coefficient in high temperature range remarkably increases. The thermal conductivity of SiO2/β-Zn4Sb3 nanocomposite material with 12 nm of SiO2 shell is the lowest and only 0.56 W·m^-1·K^-1 at 460 K. As a result, the ZT value of the SiO2/β-Zn4Sb3 nanocomposite material reaches 0.87 at 700 K and increases by 30%.

Thermoelectric properties of Bi_(1.5)Pb_(0.5)Sr_(2-x)La_xCo_2O_y polycrystalline materials

Polycrystalline samples of Bi 1.5 Pb 0.5 Sr 2-x La x Co 2 O y （x = 0.1, 0.2, 0.3） with a layered structure were prepared by solid-state reaction method. All samples are p-type semiconductors. The thermoelectric properties, namely, the electric resistivity （ρ）, Seebeck coefficient （S）, and power factor （S 2 /ρ） of the samples are dependent on chemical composition. The values of ρ, S, and S 2 /ρ increase with an increase in temperature for all samples. The substitution of Pb 2＋ for Bi 3＋ and La 3＋ for Sr 2＋ improves the thermoelectric properties of the Bi 2 Sr 2 Co 2 O y system owing to the simultaneous decrease of electric resistivity and increase of Seebeck coefficient. As a result, the optimal thermoelectric property has been obtained in Bi 1.5 Pb 0.5 Sr 1.7 La 0.3 Co 2 O y and the power factor can reach 2.1 × 10-4 W·m-1 K-2 at 998 K.

Effects of Al Addition on the Thermoelectric Properties of Zn-Sb Based Alloys

The β-Zn4Sb3, emerged as a compelling p-type thermoelectric material, is widely used in heat-electricity conversion in the 400-650 K range. In order to probe the effects of slight doping on the crystal structure and physical properties, we prepared the samples of Al-added Zn-Sb based alloys by spark plasma sintering and evaluated their microstructures and thermoelectric properties. After a limited A1 addition into the Zn-Sb based alloys we observed many phases in the alloys, which include a major phase β-Zn4Sb3, intermetallic phases ZnSb and A1Sb. The major β-Zn4Sb3 phase plays a fundamental role in controlling the thermoelectric performance, the precipitated phases ZnSb and AISb are of great importance to tailor the transport properties, such as the gradual enhancement of lattice thermal conductivity, in spite of an increased phonon scattering in additional grain boundaries. The highest thermoelectric figure of merit of 0.55 is obtained for the alloy with a limited A1 addition at 653 K, which is 0.08 higher than that of un-doped β-Zn4Sb3 at the corresponding temperature. Physical property experiments indicate that there is a potentiality for the improvement of thermoelectric properties if a proper elemental doping is carried out into the Zn-Sb based alloys, which was confirmed by A1 addition in the present work.

Effect of Y(Yttrium) Filling Fraction on Thermoelectric Properties of p-type Y_yFe_xCo_(4-x)Sb_(12)

Yttrium-filled sku, tterudites Yy Fex Co4-x Sb12 （ Y =0- 0. 40 ） were synthesized. The effect of Y filling fraction on thermoelectric properties of Yy Fex Co4-x Sb12 was investigated. All samples showed p-type conduct. The electrical conductivity decreased with increasing filling fraction y. The Seebeck coefficient inreased with increasing temperature. The lattice thermal conductivity decreased with increasing filling fraction y and showed the minimum value at a certain filling fraction y = 0.3. The effect of different filling atoms M（ M： Ba, Ce, Y） on the lattice thermal conductivity of MyFexCo4-xSb12 was discussed. The maximum ZT value of O. 7 was obtained for Y0.06 Fe0.7 Co3.3 Sb12 at 750 K.

Effects of Thickness and Temperature on Thermoelectric Properties of Bi2Te3-Based Thin Films

Bi_2Te_3 thin films and GeTe/B_2Te_3 superlattices of different thicknesses are prepared on the silicon dioxide substrates by magnetron sputtering technique and thermally annealed at 573 K for 30 min. Thermoelectric（TE）measurements indicate that optimal thickness and thickness ratio improve the TE performance of Bi_2Te_3 thin films and GeTe/B_2Te_3 superlattices, respectively. High TE performances with figure-of-merit（ZT） values as high as 1.32 and 1.56 are achieved at 443 K for 30 nm and 50 nm Bi_2Te_3 thin films, respectively. These ZT values are higher than those of p-type Bi_2Te_3 alloys as reported. Relatively high ZT of the GeTe/B_2Te_3 superlattices at 300-380 K were 0.62-0.76. The achieved high ZT value may be attributed to the unique nano-and microstructures of the films,which increase phonon scattering and reduce thermal conductivity. The results indicate that Bi_2Te_3-based thin films can serve as high-performance materials for applications in TE devices.

Theoretical study on electronic structure and thermoelectric properties of PbS_xTe_(1-x)(x = 0.25, 0.5, and 0.75) solid solution

The electronic structure and thermoelectric（TE） properties of PbS_xTe_（1-x）（x = 0.25, 0.5, and 0.75） solid solution have been studied by combining the first-principles calculations and semi-classical Boltzmann theory. The special quasirandom structure（SQS） method is used to model the solid solutions of PbS_xTe_（1-x）, which can produce reasonable electronic structures with respect to experimental results. The maximum zT value can reach 1.67 for p-type PbS0.75Te0.25 and 1.30 for PbS0.5Te0.5 at 800 K, respectively. The performance of p-type PbS_xTe_（1-x） is superior to the n-type ones, mainly attributed to the higher effective mass of the carriers. The z T values for PbS_xTe_（1-x） solid solutions are higher than that of pure Pb Te and Pb S, in which the combination of low thermal conductivity and high power factor play important roles.

Thermoelectric Properties of n-type Full-Heusler Fe_(2-2x)Co_(2x) TiSn Prepared by an Ultra-fast Synthesis Process

Full-Heusler alloy Fe_(2)TiSn was predicted to be a potential thermoelectric material with high mechanical properties and stability.Fe_(2)TiSn was usually prepared by arc-melting followed by annealing for 2 weeks,which takes a long time and consumes a large amount of energy.In this paper,Fe_(2)TiSn was prepared by an ultra-fast method,self-propagating high-temperature synthesis (SHS) combined with spark plasma sintering.The bulk materials with uniform element distribution,well controlled composition and relative densities of over 97.5% were prepared.The undoped Fe_(2)TiSn samples show p-type transport behavior.Co was heavily doped at the Fe site to prepare n-type Fe_(2-2x)Co_(2x) TiSn samples.The thermoelectric properties measurements carried out on the Co-doped samples show a highest ZT=0.02 at 300 K,which is about tripe the performance of the pristine Fe_(2)TiSn.This study provides a new approach for the rapid and low-cost preparation of full-Heusler thermoelectric materials.