Machine learning (ML) has emerged as a powerful approach for accelerating the discovery of thermoelectric (TE) materials, yet many models suffer from limited generalizability. Here we present a robust ML framework for predicting the thermoelectric figure of merit (zT) in half-Heusler (hH) compounds, emphasizing prediction of previously unseen compositions. A principal component analysis (PCA)-based train/test splitting strategy is introduced to generate representative partitions of chemical space. Bayesian hyperparameter optimization is combined with correlation-based k-best feature selection for Random Forest, XGBoost, and Neural Network models, together with the interpretable SISSO symbolic-regression method. Relative to the full set of 118 input features, the optimized feature subsets reduce the test RMSE by 16-27%. SHAP and SISSO analyses identify temperature, A-site dopant concentration, and A-site heat of vaporization as the most important descriptors of zT. The framework is validated through prediction of previously unexplored compositions, recovery of literature-reported optimal zT values for established hH systems, and first-principles calculations for the new compounds CeCoBi and CeIrBi, which exhibit favorable electronic transport properties. The framework is further applied to high-throughput screening of the doped hH chemical space, covering about 2.46 million elemental substitution combinations across 631 thermodynamically screened parent matrices under stability constraints. This screening yields a concise set of promising candidates for future study. Overall, the work establishes a generalizable workflow for reliable data-driven thermoelectric materials discovery.
Half-Heusler alloys such as the (Zr,Hf)NiSn intermetallic compounds are important thermoelectric materials for converting waste heat into electricity. Reduced electrical resistivity at the hot interface between the half-Heusler material and a metal contact is critical for device performance, however this has yet to be achieved in practice. Recent experimental work suggests that a coherent interface between half-Heusler and full-Heusler compounds can form due to diffusion of transition metal atoms into the vacant sublattice of the half-Heusler lattice. We study theoretically the structural and …
Thermoelectricity is a promising avenue for harvesting energy but large-scale applications are still hampered by the lack of highly-efficient low-cost materials. Recently, Fe$_2YZ$ Heusler compounds were predicted theoretically to be interesting candidates with large thermoelectric power factor. Here, we show that under doping conditions compatible with thermoelectric applications, these materials are prone to an unexpected magnetic instability detrimental to their thermoelectric performance. We rationalize the physics at the origin of this instability, provide guidelines for avoiding it and d…
Half-Heusler compounds usually exhibit relatively higher lattice thermal conductivity that is undesirable for thermoelectric applications. Here we demonstrate by first-principles calculations and Boltzmann transport theory that the BiBaK system is an exception, which has rather low thermal conductivity as evidenced by very small phonon group velocity and relaxation time. Detailed analysis indicates that the heavy Bi and Ba atoms form a cage-like structure, inside which the light K atom rattles with larger atomic displacement parameters. In combination with its good electronic transport propert…
We have performed systematic density functional calculations and evaluated thermoelectric properties, See- beck coefficient and anomalous Nernst coefficient of half-Heusler comounds CoMSb(M=Sc, Ti, V, Cr, and Mn). The carrier concentration dependence of Seebeck coefficients in nonmagnetic compounds are in good agreement with experimental values. We found that the half-metallic ferromagnetic CoMnSb show large anomalous Nernst effect originating from Berry curvature at the Brillouin zone boundary. These results help to understanding for the mechanism of large anomalous Nernst coefficient and giv…
Half-Heusler compounds (space group Fm3m) has garnered increasing attention in recent years in the thermoelectric community. Three decades ago, refractory RNiSn half-Heusler compounds (R represents refractory metals such as Hf, Zr, Ti) were found to be narrow-gap semiconductors with large Seebeck coefficients in 100s of micro-volt per Kelvin. Today, half-Heusler (HH) compounds have emerged as promising thermoelectric materials in the intermediate temperature range (400-800oC). HH materials are endowed with good thermal stability and scalability. Thermoelectric n-p modules based on HH materials…
Intermetallic semiconductors with the cubic Half-Heusler structure (XYZ) have excellent thermoelectric properties. This has been attributed to the high degeneracy of the carrier pockets in the band structure, but large differences are found between different material compositions. Half-Heuslers are often interpreted within Zintl chemistry, making a clear distinction between an electropositive cation ($X^{n+}$) and an extended polyanion ($YZ^{n-}$). Based on quantitative real space chemical bonding analysis, we unravel large degrees of covalent bonding between the formal cation and anion, makin…
The electronic structure and thermoelectric properties of ZrRuTe-based Half-Heusler compounds are studied using density functional theory (DFT) and Boltzmann transport formalism. Based on rigorous computations of electron relaxation time $τ$ considering electron-phonon interactions and lattice thermal conductivity $κ_l$ considering phonon-phonon interactions, we find ZrRuTe to be an intrinsically good thermoelectric material. It has a high power factor of $\sim 2\times 10^{-3}$ W/m-K$^{2}$ and low $κ_l\sim 10$ W/m-K at 800 K. The thermoelectric figure of merit $ZT \sim 0.13$ at 800 K is higher…
We report on the high-temperature (350 K <T< 1000 K) thermoelectric properties of the ternary compounds LuNiSb (cubic) and LuNiSn (orthorhombic) and a composite material (LuNiSb)$_{0.5}$(LuNiSn)$_{0.5}$. The electrical conductivity in LuNiSn is metallic, while it is semiconducting-like in LuNiSb. The Seebeck coefficient reaches -5.5 $μ$V/K at 700 K for the former compound and 66 $μ$V/K at 607 K for the latter one. The composite sample (LuNiSb)$_{0.5}$(LuNiSn)$_{0.5}$ constructed from orthorhombic matrix with cubic inclusions combines the electrical conductivity of LuNiSn with the thermoelectri…
To understand the unexpectedly high thermoelectric performance observed in the thin-film Heusler alloy Fe$_2$V$_{0.8}$W$_{0.2}$Al, we study the magnon drag effect, generated by the tungsten based impurity band, as a possible source of this enhancement, in analogy to the phonon drag observed in FeSb$_2$. Assuming that the thin-film Heusler alloy has a conduction band integrating with the impurity band, originated by the tungsten substitution, we derive the electrical conductivity $L_{11}$ based on the self-consistent t-matrix approximation and the thermoelectric conductivity $L_{12}$ due to mag…
Half-Heusler phases (space group F43m, C1b) have recently captured much attention as promising thermoelectric materials for heat-to-electric power conversion in the mid-to-high temperature range. The most studied ones are the RNiSn-type half-Heusler compounds, where R represents refractory metals Hf, Zr, and Ti. These compounds have shown a high-power factor and high-power density, as well as good material stability and scalability. Due to their high thermal conductivity, however, the dimensionless figure of merit (zT) of these materials has stagnated near 1 for a long time. Since 2013, the ve…
A half-Heusler material FeNb$_{0.8}$Ti$_{0.2}$Sb has been identified as a promising thermoelectric material due to its excellent thermoelectric performance at high temperatures. The origins of the efficient thermoelectric performance are investigated through a series of low-temperature (2 - 400 K) measurements. The high data coherence of the low and high temperatures is observed. An optimal and nearly temperature-independent carrier concentration is identified, which is ideal for the power factor. The obtained single type of hole carrier is also beneficial to the large Seebeck coefficient. The…
A series of full-Heusler alloys, $\rm Fe_2V_{1-x}W_xAl$, $0 \leq x \leq 0.2$, was prepared, characterized and relevant physical properties to account for the thermoelectric performance were studied in a wide temperature range. Additionally, off-stoichiometric samples with similar compositions have been included, and a 10~\% improvement of the thermoelectric figure of merit was obtained. The V/W substitution causes i) a change of the main carrier type, from holes to electrons as evidenced from Seebeck and Hall measurements and ii) a substantial reduction of the lattice thermal conductivity due …
We investigated six heavy element bismuth-based 18-VEC half-Heusler alloys CoTiBi, CoZrBi, CoHfBi, FeVBi, FeNbBi, and FeTaBi by first principles approach, in search of better thermoelectric prospects. The motivation is driven by expected lower thermal conductivity and the recent discovery of CoZrBi-based materials. Significantly, our calculated power factor values of all the systems show an increment of $\sim$40\% in comparison to the reported \textit{p}-type CoTiSb. We propose that doping at Bi-site, on account of electronic features, will be helpful in achieving the proposed power factor val…
Utilizing a material in thermoelectric applications requires a mechanical, thermal, and lattice stability as well a high figure of merit (ZT). In this work, we present the structural, electronic, magnetic, mechanical, thermodynamic, dynamic, and thermoelectric properties of CoFeYGe (Y = Ti, Cr) quaternary Heusler compounds using the density functional theory (DFT). The calculated mechanical properties and phonon dispersions reveal that the structures of these compounds are stable. Both CoFeCrGe and CoFeTiGe compounds show a ferromagnetic and ferrimagnetic half-metallic behavior with band gaps …
On the basis of density functional theory and semi-classical Boltzmann theory, we have investigated the structural, elastic, electronic, optical and thermoelectric properties of 18--valence electron count rhodium based half-Heusler alloys focusing on RhTiP, RhTiAs, RhTiSb, and RhTiBi. The absence of imaginary frequencies in the phonon dispersion curve for these system verifies that they are structurally stable. RhTiP is ductile in nature, while others are brittle. The alloys are found to be semiconducting with indirect band gaps ranging from 0.94 to 1.01 eV. Our calculations suggest these mate…
Polycrystalline samples of Er$_{1-x}$Ho$_x$NiSb ($x$ = 0, 0.2, 0.3, 0.5, 0.7, 0.8, 1) were characterized by means of x-ray powder diffraction (XRD), scanning electron microscopy (SEM), and optical metallography. The results proved the formation of half-Heusler alloys in the entire composition range. Their electrical transport properties (resistivity, thermoelectric power) were studied in the temperature interval 350-1000 K. The measured electrical resistivity spanned between 5 and 25 $μΩ$m. The maximum thermopower of 50-65 $μ$V/K was observed at temperatures 500-650 K. Replacing Ho for Er resu…
High lattice thermal conductivity in half-Heusler alloys has been the major bottleneck in thermoelectric applications. Disordered half-Heusler alloys could be a plausible alternative to this predicament. In this paper, utilizing first-principles simulations, we have demonstrated the low lattice thermal conductivity in two such phases, NbFe$_{0.5}$Ni$_{0.5}$Sn and TaFe$_{0.5}$Ni$_{0.5}$Sn, in comparison to well-known half-Heusler alloy TiCoSb. We trace the low thermal conductivity to their short phonon lifetime, originating from the interaction among acoustic and low-lying optical phonons. We r…
Half-Heuslers, an emerging thermoelectric material group, has complex bandstructures with multiple bands that can be aligned through band engineering approaches, giving us an opportunity to improve their power factor. In this work, going beyond the constant relaxation time approximation, we perform an investigation of the benefits of band alignment in improving the thermoelectric power factor under different density of states dependent scattering scenarios. As a test case we consider the Co-based p-type half-Heuslers TiCoSb, NbCoSn and ZrCoSb. First, using simplified effective mass models comb…
We have performed a comprehensive set of first principles calculations to study the structural, elastic, electronic, magnetic and transport properties of new quaternary Heusler compounds CoZrMnX (X =Al, Ga, Ge, In). The results showed that all the quaternary Heusler compounds were stable in Type(I) structure. CoZrMnX are elastically stable and relatively hard materials. CoZrMnAl, CoZrMnGa, and CoZrMnIn are found to be ductile and CoZrMnGe is brittle in nature. The calculated Debye temperatures of all compounds are relatively high. The electronic structure calculations reveal that CoZrMnAl is n…
Chemical doping is one of the most important strategies for tuning electrical properties of semiconductors, particularly thermoelectric materials. Generally, the main role of chemical doping lies in optimizing the carrier concentration, but there can potentially be other important effects. Here, we show that chemical doping plays multiple roles for both electron and phonon transport properties in half-Heusler thermoelectric materials. With ZrNiSn-based half-Heusler materials as an example, we use high-quality single and polycrystalline crystals, various probes, including electrical transport m…
First principle study of electronic, magnetic and thermoelectric properties of Co$_2$YPb (Y = Tc, Ti, Zr and Hf) full Heusler: Application to embedded automotive systems
We have explored the mechanical, electronic, optical and thermoelectric properties of p-type half-Heusler compound BaAgP for the first time using density functional theory based calculations. The mechanical and dynamical stability of this compound is confirmed by studying the Born stability criteria and phonon dispersion curve, respectively. It is soft, ductile and elastically anisotropic. The atomic bonding along a-axis is stronger than that along c-axis. The calculated electronic structure reveals that the studied compound is an indirect band gap semiconductor. The analysis of charge density…
Structural, electronic, and transport properties of ScNiSb, ScPdSb, and ScPtSb were investigated from first principles. Electronic band structures derived within the fully relativistic MBJLDA approach were compared with those obtained from the standard GGA calculations. All the compounds studied exhibit indirect narrow band gaps (0.24-0.63 eV). The effective masses of hole-like carriers are relatively small (0.27-0.36), and decrease with an increasing atomic number of the transition metal component. The carrier relaxation time, required for realistic calculations of the electrical conductivity…
We report $^{59}$Co, $^{93}$Nb, and $^{121}$Sb nuclear magnetic resonance (NMR) measurements combined with density functional theory (DFT) calculations on a series of half-Heusler semiconductors, including NbCoSn, ZrCoSb, TaFeSb and NbFeSb, to better understand their electronic properties and general composition-dependent trends. These materials are of interest as potentially high efficiency thermoelectric materials. Compared to the other materials, we find that ZrCoSb tends to have a relatively large amount of local disorder, apparently antisite defects. This contributes to a small excitation…
Calculations using density functional theory (DFT) were performed to investigate the structural, dynamical, mechanical, electronic, magnetic, and thermoelectric properties of VTiRhZ (Z = Al, Ga, In) alloys. The most stable structure of these alloys was found to be the type-I configuration. Using GGA-PBE functional, VTiRhGa, and VTiRhIn alloys are predicted as half-metallic ferromagnets with a 100% spin-polarization and a total magnetic moment of 3μB, which is promising for spintronic applications. The thermoelectric properties and lattice thermal conductivity of VTiRhZ alloys were obtained usi…
Half-Heusler compounds have emerged as promising thermoelectric materials that offer huge compositional space to tune their thermoelectric performance. A class of stable half Heusler compounds formed from elements of three specific groups in the periodic table viz. X$_{p}$X$'_{1-p}$Y$_{q}$Y$'_{1-q}$Z$_{r}$Z$'_{1-r}$ (with X, X$'$= Ti, Zr, Hf, Y, Y$'$ = Ni, Pd, Pt and Z, Z$'$ = Ge, Sn, Pb and p, q, r = 0, 0.25, 0.75 and 1) via various stoichiometric isoelectronic elemental substitution at the X, Y and Z sites respectively is investigated. Intelligent filters are employed at each step of our hig…
Half-Heusler (HH) phases have garnered much attention as thermally stable and non-toxic thermoelectric materials for power conversion. The most studied alloys to date utilize Hf, Zr, and Ti as the base components. These alloys can achieve a moderate dimensionless figure of merit, ZT, near 1. Recent studies have advanced the thermoelectric performance of HH alloys by employing nanostructures and novel compositions to achieve larger ZT, reaching as high as 1.5. Herein, we report that traditional alloying techniques applied to the conventional HfZr-based half-Heusler alloys can also lead to excep…
There is an increasing reckoning that the thermoelectric performance of a material is dependent on its microstructure. However, the microstructure-properties relationship often remains elusive, in part due to the complexity of the hierarchy and scales of features that influence transport properties. Here, we focus on the promising Heusler-Fe2VAl compound. We directly correlate microstructure and local properties, using advanced scanning electron microscopy methods including in-situ four-point-probe technique for electron transport measurements. The local thermal conductivity is investigated by…
Science-driven design of future thermoelectric materials requires a deep understanding of the fundamental relationships between microstructure and transport properties. Grain boundaries in polycrystalline materials influence the thermoelectric performance through the scattering of phonons or the trapping of electrons due to space-charge effects. Yet, the current lack of careful investigations on grain boundary-associated features hinders further optimization of properties. Here, we study n-type NbCo1-xPtxSn half-Heusler alloys, which were synthesized by ball milling and spark plasma sintering …
Ternary half Heusler alloys are under intense investigations recently towards achieving high thermoelectric figure-of-merit (ZT). Of particular interest is the ZrNiPb based half Heusler (HH) alloy where an optimal value of ZT = 0.7 at 773 K has been achieved by co-doping Sn and Bi at Pb site. In this work, we identify an excellent ZT of 1.3 in ZrNi1+xPb0.38Sn0.6Bi0.02 (x= 0.03, at 773 K) composite alloy. This is achieved by synergistic modulation of electronic as well as thermal properties via introduction of minor phase of full Heusler (FH) in the HH matrix through compositional tuning approa…
We investigate the high temperature thermoelectric properties of Heusler alloys Fe2-xMnxCrAl (0<x<1). Substitution of 12.5% Mn at Fe-site (x = 0.25) causes a significant increase in high temperature resistivity (\r{ho}) and an enhancement in the Seebeck coefficient (S), as compared to the parent alloy. However, as the concentration of Mn is increased above 0.25, a systematic decrement in the magnitude of both parameters is noted. These observations have been ascribed (from theoretical analysis) to a change in band gap and electronic structure of Fe2CrAl with Mn-substitution. Due to absence of …
