Half Heusler Research Articles

First-Principles Insights into Thermoelectric Behavior of XNiAs (X = Sc, Y) Half-Heusler Compounds

Abstract Half-Heusler (HH) compounds are regarded as potential candidates for thermoelectric devices to convert waste heat energy into electrical power, which could help mitigate the ongoing energy crisis. In this study, we investigate the structural, electronic, magnetic, and thermoelectric properties of hH compounds XNiAs (X = Sc, Y) using Density Functional Theory (DFT) and semi-classical Boltzmann
transport theory (BTE). The compounds are non-magnetic semiconductors with an indirect band gap of 0.48 ( 0.50) eV for ScNiAs (YNiAs) respectively. Both materials show dynamic and mechanical stability, with ScNiAs displaying brittleness and YNiAs exhibiting ductility. At room temperature, the lattice thermal conductivity (κl ) for ScNiAs is 28.67 W/mK, while for YNiAs, it is 15.21 W/mK and
both decrease as the temperature rises. The highest value of power factors is 29.03 µW/cmK2 and 29.74 µW/cmK2 for ScNiAs and YNiAs respectively at 1100 K for n-type doping. The optimal values of the figure of merit (zT) for n-type doping are 0.33 for ScNiAs and 0.58 for YNiAs at 1100 K. Both compounds exhibit better thermoelectric performance for n-type doping compared to p-type doping.
The presence of flat bands and higher κl limits these materials from achieving higher zT values.

Exploring the electronic, magnetic and thermoelectric properties of TbPtBi half-Heusler: DFT study

Abstract In this investigation, we employed density functional theory to scrutinize the structural, electronic, magnetic, thermoelectric, and phonon properties of the topological half-Heusler (HH) TbPtBi compound. The stable phonon dispersion spectrum affirms the dynamical stability of the compound. The inclusion of spin-orbit coupling (SOC) significantly influenced the compound’s electronic and thermoelectric properties. The density of state (DOS) confirmed the impact of SOC on the topologically non-trivial metallic behavior of TbPtBi under the equilibrium lattice constant. The SOC altered the DOS at the Fermi level, leading to band splitting and a notable 70% reduction in state density. The Tb-4f electrons in the compound induce total magnetization in AFM (−5.93 µB/cell) and FM (5.94 µB/cell) phases, while SOC eliminates this magnetization. The thermoelectric performance of TbPtBi under compressive and tensile strain has been systematically studied. The result indicate that compressive strain causes a notable increment in Seebeck coefficient and Power factor (20.4 × 1011 W K−2 m−1) of this compound at room temperature. High thermoelectric performance under compressive strain in the HH compound TbPtBi might open new avenues for investigating other topological thermoelectric materials.

Improved thermoelectric properties of n-type ZrNiCu0.05Sn by doping Y2O3

Half-Heusler (HH)-based alloys are promising candidates for high-temperature thermoelectric (TE) energy conversion materials due to their excellent adaptability in high-temperature regions (900 - 1100 K). However, their TE performance is greatly limited owing to the inherently high lattice thermal conductivity (κl). In this study, we introduce a synergistic strategy to reduce thermal conductivity while modifying electrical transport properties through yttrium oxide (Y2O3) dispersion. The binary NiSn compound precipitations with sub-micron dimension together with Y2O3 nanoparticles synergistically intensify the phonon scattering and enhance the seebeck coefficient (S) effectively via energy filtering effect (EFE) at hetero-interfaces, leading to a remarkable reduction in κl and a slight improvement in the power factor (PF). Consequently, upon 1.5 wt% Y2O3 introduction, the sample incorporating Y2O3 exhibits a ∼13% reduction in total thermal conductivity (κt) as compared to the HH matrix, reaching a peak ZT of 0.86 at 938 K, thereby successfully optimizing its TE performance. The presented strategy provides a feasible approach to simultaneously modulate the thermal and electrical transport behaviors to improve the TE performance of HH-based materials.

Ferrimagnetic half metals TaMnZ (Z = As, Sb, Bi) for thermoelectric and spintronic applications – Material computations

Half metals possess coupling behavior of metals and semiconductors with wide heat transport and spin transport properties. This research article covers the structural, mechanical, electronic, magnetic and thermoelectric properties of the half Heusler alloys TaMnZ (Z = As, Sb, Bi). The equilibrium lattice constants and corresponding ground state energies show that the studied alloys are stable in the ferrimagnetic cubic phase. The band dispersion plots suggest that the compounds TaMnAs, TaMnSb and TaMnBi are half metals with indirect band gap having the band gap energies of 1.13 eV, 1.24 eV and 1.12 eV respectively in the spin down channel. As the materials have 100 % spin polarization with an integer magnetic moment of −1 μB, they are suitable for making spintronic devices such as spin transistors and spin-flip flops. The temperature-dependent thermoelectric properties of the alloys have been studied by classical Boltzmann theory. The materials have low lattice thermal conductivity which was confirmed by Slack’s equation. The obtained thermoelectric figure of merit for p-type TaMnAs, TaMnSb and TaMnBi is 0.7, 0.6 and 0.8 respectively at 1200 K. Similarly, the figure of merit obtained for n-type TaMnAs, TaMnSb and TaMnBi is 0.6, 0.64 and 0.8 respectively at the same temperature. The favourable heat and spin transport properties of these alloys show that they are the potential characters to figure out better thermoelectric and spintronic performance.

Effect of Pressure on Thermoelectric Performance of Half Heusler Compounds

In this work, the density functional theory (DFT) combined with Boltzmann transport equations are used to explore the effect of pressure on the structural, mechanical, thermal, and electronic properties of two half Heusler compounds PdXSn (X = Zr,Hf). The electronic band structure is tuned under pressure which enhances the thermoelectric properties of both compounds. The band gap opens with pressure and its value is 0.91 eV (1.26) for PdZrSn and 0.82 eV (1.16 eV) for PdHfSn at 0GPa (30GPa). The indirect nature does not alter at any pressure. The seebeck coefficient enhances from 900 μV/K to 1161 μV/K for PdZrSn and from 763 μV/K to 1012 μV/K for PdHfSn at pressure 0GPa to 30GPa. Similar trends observed in case of electrical conductivity and electronic part of thermal conductivity. But the lattice thermal conductivity is reduced from15.16 W/mKto 12.51 W/mK for PdZrSn and from 9.53 W/mK to 8.34 W/mK for PdHfSn at 30GPa respectively. Overall, the figure of merit ZT is elevated and attained maximum value of 0.45(0.55) for PdZrSn (PdHfSn) under pressure up to 30GPa.

Enhanced optoelectronic and thermoelectric properties of half Heusler compounds KXSb (X = Be, Mg, Ca and Sr): A first principle study

In the present paper, structural, electronic, elastic, thermodynamic, optical, and thermoelectric properties of h-H alloys KXSb (X = Be, Mg, Ca, and Sr) are investigated for the first time. These properties were explored using quantum mechanical model – the density functional theory (DFT) with both GGA-PBE and TB-mBJ exchange-correlation functional. The Boltzmann transport equations and the Full Potential Linearized Augmented Plane wave (FP-LAPW) approach, as built into the WIEN2k code, are used to investigate these properties. The band structures and density of states (DOS) are also studied. The half-Heusler compounds show semiconductor properties with both the GGA and mBJ methods, while the KBeSb alloy exhibits metallic nature under the GGA-PBE approach. The elastic and thermo dynamical properties were also investigated, and the results revealed that the compounds are mechanically and thermally stable. The observed high Debye temperature (ϴD) implies that the alloy is harder and possesses a significant Debye sound velocity. The current paper highlights the optical and thermoelectric applications of the alloys. At 900 K, KCaSb exhibits maximum power factors of 8.83 × 1011 (W/mK2s) with the GGA-PBE method and 8.19 × 1011 (W/mK2s) with the TB-mBJ approach.

Strategic Design and Mechanistic Understanding of Vacancy-Filling Heusler Thermoelectric Semiconductors.

Doping narrow-gap semiconductors is a well-established approach for designing efficient thermoelectric materials. Semiconducting half-Heusler (HH) and full-Heusler (FH) compounds have garnered significant interest within the thermoelectric field, yet the number of exceptional candidates remains relatively small. It is recently shown that the vacancy-filling approach is a viable strategy for expanding the Heusler family. Here, a range of near-semiconducting Heuslers, TiFexCuySb, creating a composition continuum that adheres to the Slater-Pauling electron counting rule are theoretically designed and experimentally synthesized. The stochastic and incomplete occupation of vacancy sites within these materials imparts continuously changing electrical conductivities, ranging from a good semiconductor with low carrier concentration in the endpoint TiFe0.67Cu0.33Sb to a heavily doped p-type semiconductor with a stoichiometry of TiFe1.00Cu0.20Sb. The optimal thermoelectric performance is experimentally observed in the intermediate compound TiFe0.80Cu0.28Sb, achieving a peak figure of merit of 0.87 at 923 K. These findings demonstrate that vacancy-filling Heusler compounds offer substantial opportunities for developing advanced thermoelectric materials.

Developing advanced CrSi coatings for combatting surface degradation of N-type (Zr,Ti)Ni(Sn,Sb) and P-type (Zr,Ti)Co(Sn,Sb) half Heusler thermoelectric materials

In this study, advanced oxidation-protective CrSi coatings were developed and deposited on N-type (Zr,Ti)Ni(Sn,Sb) and P-type (Zr,Ti)Co(Sn,Sb) thermoelectric (TE) materials using an environmentally friendly closed field unbalanced magnetron sputtering PVD system. The oxidation behaviour of the CrSi-coated and uncoated samples was evaluated through static oxidation tests at 500 °C and 600 °C for 10h and 50 h, respectively. In addition, the samples were exposed to cyclic oxidation tests between 25 °C and 500 °C for 10, 30 and 50 cycles, with each cycle consisting of 1h of oxidation at 500 °C, to examine the coating ability to withstand thermal shock, which is involved in the service of TE devices. The surface morphology, cross-section layer structure, elemental distribution and phase constitution were analysed using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDX) and X-ray diffraction (XRD). The mass gain after the oxidation tests was measured and calculated for each sample to study the oxidation kinetics. The uncoated samples exhibited a considerable amount of oxidation, leading to change in the surface morphologies, and the formation of alternated layers including oxide products (Zr(Ti)O2, SnO2) and Ni3Sn4 compound for the N-type and (Zr(Ti)O2, SnO2, Sb2O4) and CoSb compound for the P-type material, after static and cyclic oxidation tests. The experimental work in this study has, for the first time, demonstrated that the CrSi coatings developed with very high thermal stability and oxidation resistance can effectively protect both the N-type and P-type materials from oxidation and sublimation even during cyclic oxidation tests. The strong affinity of Cr and Si to oxygen can trap oxygen, retard its inward diffusion and thus protect the TE material substrate from oxidation. This finding could pave the way towards the further development of long-life high-performance TE generators and devices, thus contributing to the net zero target.

Ab initio analysis of structural, electronic, magnetic, thermodynamic, and elastic properties of Half Heusler alloys ZMnAs (Z = Be, Mg) for spintronics applications

In this study, the structural, electronic, magnetic, thermodynamic, and elastic attributes of ZMnAs (Z = Be, Mg) have been investigated. These Half-Heusler alloys exhibit stability in the ferromagnetic state (FM), as demonstrated by optimization-related energy release. The half-metallicity (HM) of these compounds is examined through the band structures and density of states (DOS). In addition, the crystal field and exchange energies are reported to confirm the control of electron spin. Additionally, the double exchange process and exchange constants were premeditated. In this case, ferromagnetism (FM) is caused by the quantum exchange of electrons, as evidenced by the negative pd exchange energy and the exchange constants, rather than being a result of clustering effects. The quasi-harmonic Debye model, included within the Gibbs code, was utilized to calculate the thermodynamic properties. These two compounds are mechanically stable and show ductile nature confirmed by the value of Poisson's ratio (v), Pugh's ratio (B/G), and Cauchy pressure (CP), which demonstrates the ability to withstand substantial plastic deformation before fracturing. Based on our calculations, the half-metallic (HM) nature, thermodynamic, ferromagnetic, ductile, and high inherent magnetic moment have been evaluated. These alloys are crucial in the advancement of spintronics and renewable energy systems.

Investigation of the structural, mechanical, anisotropic, thermal conductivity, electronic, and phonon properties of RhTiZ(Z: As, sb) half heusler compounds under high pressure: A DFT study

This investigation delves into the effects of pressure on the structural, elastic, thermal conductivity, anisotropy, electronic, and phonon properties of the RhTiZ (Z: As, Sb) compound, characterized by a half-Heusler structure, employing the first-principles method. Parameters such as lattice constant, volume, density, bulk modulus, the first derivative of the bulk modulus, and energy were meticulously scrutinized at zero pressure, drawing comparisons with theoretical and experimental data and existing literature. Throughout all pressure values, RhTiZ (Z: As, Sb) compounds exhibit robust structural stability, meeting the stringent criteria outlined by Born, with no discernible signs of instability even under heightened pressure conditions. The compound showcases ductile characteristics based on the Pugh ratio (G/B), Cauchy pressure (C12–C44, C″), and Poisson ratio (λ) criteria. Employing the VESTA program, anisotropic properties were comprehensively assessed in three dimensions, considering the influence of pressure. In terms of electronic properties, the compound maintains its semiconducting nature, resiliently preserving this trait amidst variations in pressure. The absence of negative frequencies in the phonon distribution curve serves as a testament to the dynamic stability inherent in the compound. Finally, a comprehensive evaluation was conducted to delineate the repercussions of pressure on both the physical and electronic attributes of the RhTiZ (Z: As, Sb) compound, which holds promise for applications in thermal insulation materials.

Disclosing magnetic clusters in the metallic half-Heusler ferromagnet Cr4PtGa17 with a breathing pyrochlore lattice

We report a ferromagnetic resonance (FMR) study of a single crystal of Cr4PtGa17, the first material of a half-Heusler (HH) type with a metallic ferromagnetic breathing pyrochlore structure. The spatial distribution of the magnetic free energy density derived from the FMR data appears to be of a cubic symmetry despite the lower symmetry coordination of magnetic Cr ions. This surprising finding strongly suggests that the Cr4Ga14 structural unit at the Y site of the HH general XYZ formula forms an octahedrally shaped integral magnetic cluster, likely due to strong exchange interaction between the Cr ions via covalent Cr-Ga-Cr bonds. The presence of magnetic clusters within a regular metallic lattice appears to be a new intriguing characteristics of these novel types of HH compounds whereas Cr4PtGa17, at the same time, constitutes the rare example of such metallic pyrochlore-type material.

A first principles study of stability, electronic and thermoelectric characteristics of novel high temperature half- heusler alloys ScAgX (X=Si,Ge,Sn)

To meet the ever-increasing renewable energy demand Half- Heusler (HH) materials can be a potential candidate. Heusler materials are seeking popularity as efficient high-temperature thermoelectric materials. Here we systematically investigated the structural, electronic, mechanical and thermoelectric properties of novel HH compounds ScAgX (X = Si,Ge,Sn) in the framework of the first principles approach. These materials are found to be chemically, mechanically and dynamically stable. Born-Oppenheimer molecular dynamics simulations (BOMD) verify the thermal stability of these materials from 300 K to 1100 K. The semiconducting nature of these materials is confirmed by the electronic band structure. ScAgX (X = Si,Ge,Sn) have an indirect band gap of 0.37 eV, 0.42 eV and 0.38 eV respectively. A high value of Seebeck coefficient of 6351 μV/K, 6955 μV/K and 6558 μV/K has been obtained at room temperature. ScAgSi shows a high value of electrical conductivity (∼106 S/m) among these compounds at room temperature. The calculated value of the figure of merit (ZT) of ScAgX (X = Si,Ge,Sn) is 0.12, 0.08 and 0.16 at 1100 K respectively. Our present investigation shows that these materials can be a potential candidate for high-temperature thermoelectric power generation.

The A-Ni chemical bond in AIIINiSb (AIII=Sc, Y, Er) half-Heusler materials triggers the formation of anomalous vacancy defects

Defects exert a profound influence on thermoelectric materials by altering electronic band structures and significantly impacting their performance. Despite being a potentially promising thermoelectric material, the mechanism behind defect formation in half-Heusler (HH) compounds ABX remains unclear, impeding the enhancement of their thermoelectric properties. In this study, we investigated the intrinsic defect formation energies for AⅢNiSb (AⅢ = Sc, Y, Er) and other 9 HH compounds, namely AⅣNiSn (AⅣ = Ti, Zr, Hf), AⅤFeSb (AⅤ = V, Nb, Ta), and AⅣCoSb (AⅣ = Ti, Zr, Hf), using first-principles calculations and thermodynamics. The results reveal that AⅢNiSb (AⅢ = Sc, Y, Er) exhibits anomalous B (Ni) vacancy defects, with their formation energies being significantly lower than those of the corresponding B vacancy defects in the other 9 HH compounds. This anomaly can be attributed to the strength of the A-B bonds, where a decrease in bond strength leads to a decrease in the formation energy of B vacancies. This approach of exploring the influence of interatomic bond strength on defect formation is not only insightful for HH compounds but also holds potential applications in defect studies across various materials, offering a broader perspective on the fundamental mechanisms governing defect formation and stability.

The promising potential of half Heusler EuFeSb alloy for high-performance thermoelectric with improved half-metallicity and optical properties: a DFT study

The promising potential of half Heusler EuFeSb alloy for high-performance thermoelectric with improved half-metallicity and optical properties: a DFT study

A systematic first-principles investigation of the structural, electronic, mechanical, optical, and thermodynamic properties of Half-Heusler ANiX (ASc, Ti, Y, Zr, Hf; XBi, Sn) for spintronics and optoelectronics applications.

This paper is the first to look at the structural, electronic, mechanical, optical, and thermodynamic properties of the ANiX (ASc, Ti, Y, Zr, Hf; XBi, Sn) half-Heusler (HH) using DFT based first principles method. The lattice parameters that we have calculated are very similar to those obtained in prior investigations with theoretical and experimental data. The positive phonon dispersion curve confirm the dynamical stability of ANiX (ASc, Ti, Y, Zr, Hf; XBi, Sn). The electronic band structure and DOS confirmed that the studied materials ANiX (ASc, Ti, Y, Zr, Hf; XBi, Sn) are direct band gap semiconductors. The investigation also determined significant constants, including dielectric function, absorption, conductivity, reflectivity, refractive index, and loss function. These optical observations unveiled our compounds potential utilization in various electronic and optoelectronic device applications. The elastic constants were used to fulfill the Born criteria, confirming the mechanical stability and ductility of the solids ANiX (ASc, Ti, Y, Zr, Hf; XBi, Sn). The calculated elastic modulus revealed that our studied compounds are elastically anisotropic. Moreover, ANiX (ASc, Ti, Y, Zr, Hf; XBi, Sn) has a very low minimum thermal conductivity (Kmin), and a low Debye temperature (θD), which indicating their appropriateness for utilization in thermal barrier coating (TBC) applications. The Helmholtz free energy (F), internal energy (E), entropy (S), and specific heat capacity (Cv) are determined by calculations derived from the phonon density of states.

Structural, electronic, magnetic, and thermoelectric properties of half Heusler alloys ZrCo1-XFeXSb (X = 0, 0.25, 0.5, 0.75, 1): A DFT study

The structural, electronic, magnetic, and thermoelectric properties of half-Heusler alloys ZrCo1-XFeXSb (X = 0, 0.25, 0.5, 0.75, 1) are investigated using the density functional theory. It is evident that ZrCoSbis a non-magnetic semiconductor. This study investigates the influence of substituting Fe for Co on the electronic structure and magnetic characteristics of ZrCoSb. The alloys transform into half-metallic ferromagnets as Fe substitutes Co. The indirect band gap of the ZrCo1-XFeXSb alloys decreases with increasing Fe content. The phonon dispersion curve is studied to determine the structural stability. The calculated values for the elastic constant for each composition satisfy the criteria for mechanical stability. To analyse its thermoelectric properties, the semi-classical Boltzmann transport theory is used to determine the Seebeck coefficients, electrical and thermal conductivities, and power factor as a function of temperature.

Spin-polarized DFT investigations of novel KVSb half-Heusler compound for spintronic and thermodynamic applications

In this study we have investigated the robust phase stability, elasto-mechanical, thermophysical and magnetic response of KVSb half Heusler compound by implementing density functional theory (DFT) models in WIEN2k simulation package. The dynamic phase stability is computed in phase type I, II & III phase configurations by optimising their energy. It is observed that given compound is more stable in spin-polarized state of phase type-III. To explore the electronic band structure, we apply the generalised gradient approximation along with Hubbard potential U. The electronic band profile of the Heusler alloy display a half-metallic nature. Moreover, the calculated second-order elastic parameters divulge the brittle nature. To understand the thermodynamical and thermoelectric stability of the alloy at various temperature and pressures ranges Quasi-Harmonic Debye model is executed successfully. The computed value of magnetic moment (MM) found in good agreement with Slater-Pauling rule. Our findings confirms that the predicted half Heusler alloy can be used in various spintronics and thermoelectric applications.

Investigating the electronic structure, magnetic, and optical properties of the KCrS half Heusler compound from first principles

Investigating the electronic structure, magnetic, and optical properties of the KCrS half Heusler compound from first principles

Tailoring the physical characteristics of ScTaPd2Sn2 and ScTaPt2Sn2 double half-Heusler compound for thermoelectric applications

Due to its potential uses in thermoelectrics, spintronics, and other sectors, double half-Heusler compounds have recently attracted much attention. This study presents the first-ever report on the structural, electronic, optical, elastic, and thermoelectric characteristics of the double half Heusler (DHH) compounds ScTaPd2Sn2 and ScTaPt2Sn2, employing density functional theory (DFT). Using the EV-GGA approximation, the estimated band structures exhibit a semiconductor behavior with an indirect bandgap of 0.549 eV and 0.851 eV, respectively. In addition, we examined optical characteristics. Our material structural stability and stiffness were confirmed using elastic characteristics. Boltzmann’s semiclassical theory attempts to explain a simulation concept in the BoltzTrap software. According to the thermoelectric investigation, these DHH are a p-type material, a candidate for thermoelectric application, specifically when doped.

Electronic, phonon and thermoelectric properties of MnCrX (X = As, P, Sb) half Heusler alloys: a DFT study

Electronic, phonon and thermoelectric properties of MnCrX (X = As, P, Sb) half Heusler alloys: a DFT study