SnSe has drawn increasing attention in thermoelectric applications because of its exceptional n/p-type characteristics. Although recent studies have reported an excellent figure of merit (ZT) value in p-type polycrystalline SnSe, achieving a breakthrough in thermoelectric performance for its n-type counterpart SnSe remains a critical challenge. The presence of VSn imposes a critical constraint on the synergistic optimization of carrier transport and phonon scattering in n-type SnSe. In this study, liquid phase sintering introduces high-density dislocations into n-type SnSe polycrystals, effectively scattering mid-frequency phonons. Huge lattice strain fluctuations caused by the defects enable an ultralow lattice thermal conductivity (0.21 W m−1 K−1) at 793 K. In addition, part of the liquid phase Sn tends to penetrate into the matrix, which leads to a higher carrier concentration and considerable enhancement in electrical properties. Consequently, a superior ZT (~1.9, 793 K) and an outstanding average ZT (ZTave) (~0.72, 300 to 873 K) are achieved in polycrystalline SnSe, which rank at the top level reported for SnSe-based n-type thermoelectric materials, exceeding those of most n-type thermoelectric systems for mid-temperature applications.
Over the last decades, notable progress is achieved in (K, Na)NbO3 (KNN)-based lead-free piezoceramics. However, more studies are conducted to increase its piezoelectric charge coefficient (d33). For actuator applications, piezoceramics need high electric-field induced strain under low electric fields while maintaining exceptional temperature stability across a wide temperature range. In this study, this work developes Li/Sb-codoped KNN (LKNNS) ceramics with high electrostrain by defect engineering and domain engineering. A remarkable strain of 0.43%, along with a giant d33* value of 2177 pm V-1, is attained in the LKNNS ceramic at 20 kV cm-1. The ceramic exhibits a minimal performance decrease of less than 15% over a temperature range from room temperature to 150 °C. The exceptional strain is attributed to the presence of A-site vacancy-oxygen vacancy ( V A ' - V O • • ${\mathrm{V}}_{\mathrm{A}}^{{\prime}}{\mathrm{ - V}}_{\mathrm{O}}^{{\mathrm{ \bullet \bullet }}}$ ) defect dipoles and the increase in nano-domains. The hierarchical domain configuration and V A ' - V O • • ${\mathrm{V}}_{\mathrm{A}}^{{\prime}}{\mathrm{ - V}}_{\mathrm{O}}^{{\mathrm{ \bullet \bullet }}}$ defect dipoles impede the switched domains from reverting to their original state as temperature increases, furthermore, the elongated dipole moments of V A ' - V O • • ${\mathrm{V}}_{\mathrm{A}}^{{\prime}}{\mathrm{ - V}}_{\mathrm{O}}^{{\mathrm{ \bullet \bullet }}}$ caused by rising temperatures compensate for strain reduction results in exceptional temperature stability. This study provides a model for designing piezoelectric materials with exceptional overall performance under low electric fields and across a wide temperature range.
Thermoelectric Peltier coolers (PCs) are being increasingly used as temperature stabilizers for optoelectronic devices. Increasing integration drives PC miniaturization, requiring thermoelectric materials with good strength. We demonstrate a simultaneous gain of thermoelectric and mechanical performance in (Bi, Sb)2Te3, and successfully fabricate micro PCs (2 x 2 mm2 cross-section) that show excellent maximum cooling temperature difference of 89.3 K with a hot-side temperature of 348 K. A multi-step process involving annealing, hot-forging and composition design, is developed to modify the atomic defects and nano- and microstructures. The peak ZT is improved to similar to 1.50 at 348 K, and the flexural and compressive strengths are significantly enhanced to similar to 140 MPa and similar to 224 MPa, respectively. These achievements hold great potential for advancing solid-state refrigeration technology in small spaces. Superior mechanical and thermoelectric performance is simultaneously achieved in the (Bi, Sb)2Te3 nanocomposite through an innovative synthesis process, enabling the fabrication of efficient Peltier microcoolers.
Degenerate semiconductors usually demonstrate a metallic-like conduction behavior, showing limited carrier mobility at high temperatures. Herein, by incorporating B4C nanoparticles into the Cu1.99Se system, an unusual switch from the "degenerate" to "non-degenerate" semiconducting behavior is revealed as a result of the engineered interfaces. Heterogeneous interfaces and disordered Cu2Se amorphous phases are introduced in the Cu1.99Se/B4C composites, which generate a trapping effect against the mobile Cu ions, leading to a distinctive "hump" signature for electrical conductivity. Benefiting from this rare high-temperature thermoelectric response, a high power factor is obtained due to reduced carrier concentration and enhanced mobility, and low lattice thermal conductivity is retained because of relatively stronger anharmonic lattice vibrations. Consequently, the Cu1.99Se + 0.9 vol.% B4C sample at least achieves a maximum thermoelectric figure of merit (ZT) of 2.6 at 1025 K with synergistically enhanced mechanical robustness. The present interface engineering strategy may be applicable to other thermoelectric materials with ionic migration characteristics.
Abstract GeTe is a promising p-type material with increasingly enhanced thermoelectric properties reported in recent years, demonstrating its superiority for mid-temperature applications. In this work, the thermoelectric performance of GeTe is improved by a facile composite approach. We find that incorporating a small amount of boron particles into the Bi-doped GeTe leads to significant enhancement in power factor and simultaneous reduction in thermal conductivity, through which the synergistic modulation of electrical and thermal transport properties is realized. The thermal mismatch between the boron particles and the matrix induces high-density dislocations that effectively scatter the mid-frequency phonons, accounting for a minimum lattice thermal conductivity of 0.43 Wm−1K−1 at 613 K. Furthermore, the presence of boron/GeTe interfaces modifies the interfacial potential barriers, resulting in increased Seebeck coefficient and hence enhanced power factor (25.4 μWcm−1K−2 at 300 K). Consequently, we obtain a maximum figure of merit Z max of 4.0 × 10−3 K−1 at 613 K in the GeTe-based composites, which is the record-high value in GeTe-based thermoelectric materials and also superior to most of thermoelectric systems for mid-temperature applications. This work provides an effective way to further enhance the performance of GeTe-based thermoelectrics.
Over the past two decades, (K0.5Na0.5)NbO3 (KNN)-based lead-free piezoelectric ceramics have made significant progress. However, attaining a high electrostrain with remarkable temperature stability and minimal hysteresis under low electric fields has remained a significant challenge. To address this long-standing issue, we have employed a collaborative approach that combines defect engineering, phase engineering, and relaxation engineering. The LKNNS-6BZH ceramic, when sintered at Tsint = 1170 ℃, demonstrates an impressive electrostrain with a d33∗ value of 0.276% and 1379 pm·V–1 under 20 kV·cm–1, which is comparable to or even surpasses that of other lead-free and Pb(Zr,Ti)O3 ceramics. Importantly, the electrostrain performance of this ceramic remains stable up to a temperature of 125 ℃, with the lowest hysteresis observed at 9.73% under 40 kV·cm–1. These excellent overall performances are attributed to the presence of defect dipoles involving VA′–VO∙∙ and BNb′–VO∙∙, the coexistence of R–O–T multiphase, and the tuning of the trade-off between long-range ordering and local heterogeneity. This work provides a lead-free alternative for piezoelectric actuators and a paradigm for designing piezoelectric materials with outstanding comprehensive performance under low electric fields.
Cu2Se is a promising p-type thermoelectric material for energy harvesting due to its intrinsically low thermal conductivity arising from the liquid-like Cu ions, leaving very limited room for regulation of phonon propagation. Herein, the thermal conductivity of superionic Cu2Se is efficiently mediated by titanium oxide nanoclusters, leading to an exceptionally high thermoelectric figure of merit (ZT) at high temperatures. By controlling the oxygen deficiency, the sophisticated TiO2−n architectures can be constructed with optimized phase composition and electrical properties. The presence of p-n junctions helps to reduce carrier concentration without degrading mobility, and the complex heterogeneous interfaces generated by TiO2−n nanoclusters give rise to huge interfacial thermal resistance. Benefiting from the suppressed electrical transport and enhanced phonon scattering, the total thermal conductivity shows a reduction of at least 36%, contributing to a high ZT value of 2.8 at 973 K. This work demonstrates a paradigm of modulating thermal transport through the self-assembly design.
The liquid-like feature of thermoelectric superionic conductors is a double-edged sword: the long-range migration of ions hinders the phonon transport, but their directional segregation greatly impairs the service stability. We report the synergetic enhancement in figure of merit (ZT) and stability in Cu 1.99 Se-based superionic conductors enabled by ion confinement effects. Guided by density functional theory and nudged elastic band simulations, we elevated the activation energy to restrict ion migrations through a cation–anion co-doping strategy. We reduced the carrier concentration without sacrificing the low thermal conductivity, obtaining a ZT of ∼3.0 at 1,050 K. Notably, the fabricated device module maintained a high conversion efficiency of up to ∼13.4% for a temperature difference of 518 K without obvious degradation after 120 cycles. Our work could be generalized to develop electrically and thermally robust functional materials with ionic migration characteristics.
Porous structures can hinder phonon transport but inevitably deteriorate electrical and mechanical properties. In order to suppress the formation of pores, we propose a chemical bond engineering strategy to constrain the volatile Se in Cu2Se-based materials via applicable elemental substitution. Benefiting from the reduced porosity and successful dual doping, Cu vacancies and carrier mobility are optimized for the Gd2S3-added Cu1.99Se samples, leading to an ultrahigh power factor of X17.4 mW cm -1 K-2 at 1,000 K and a high figure of merit of X2.5 at 1,050 K. The fabricated segmented single -leg device maintains a high conversion efficiency of -9.0% and a power density of 636.3 mW cm -2 at DT = 516 K without obvious degradation over 110 cycles of stability tests. Our work demonstrates a paradigm to control the porosity caused by elemental volatilization, providing more opportunities to enhance both the thermoelectric performance and service stability.
Distributed hybrid flow shop scheduling problem (DHFSP) has attracted some attention. In this study, DHFSP with sequence-dependent setup times is studied and a multi-class teaching–learning-based optimization (MTLBO) is proposed to minimize makespan and maximum tardiness simultaneously. A two-string representation is adopted. s classes are formed to improve search efficiency by implementing reward and punishment mechanism among them. Class evaluation is introduced and two teacher phases and one learner phase are applied in the evolution of each class. Elimination process acts on the worst class to avoid the waste of computing resource. A number of experiments are conducted and the computational results demonstrate that MTLBO is a very competitive method for DHFSP.
Thermoelectric technology enables the direct interconversion between heat and electricity. SnSe has received increasing interest as a new promising thermoelectric compound due to its exceptionally high performance reported in crystals. SnSe possesses intrinsic low thermal conductivity as a congenital advantage for thermoelectric, but high thermoelectric performance can be hardly achieved due to the difficulty to realize efficient doping to raise its low carrier concentration to an optimal level. In this work, it is found that a series of rare earth elements are effective dopants for SnSe, which can greatly improve the electrical transport properties of p ‐type polycrystalline SnSe. In particular, the remarkable enhancement in electrical conductivity and power factor is achieved by Na/Er co‐doping at 873 K. The lattice thermal conductivity is reduced due to the presence of abundant defects (dislocations, stacking faults, and twin boundaries). Consequently, a peak thermoelectric figure of merit ZT (2.1) as well as a high average ZT (0.77) are achieved in polycrystalline SnSe.
Mg3 (Sb,Bi)2 is a potential nearly-room temperature thermoelectric compound composed of earth-abundant elements. However, complex defect tuning and exceptional microstructural control are required. Prior studies have confirmed the detrimental effect of Mg vacancies (VMg ) in Mg3 (Sb,Bi)2 . This study proposes an approach to mitigating the negative scattering effect of VMg by Bi deficiency, synergistically modulating the electrical and thermal transport properties to enhance the thermoelectric performance. Positron annihilation spectrometry and Cs -corrected scanning transmission electron microscopy analyses indicated that the VMg tends to coalesce due to the introduced Bi vacancies (VBi ). The defects created by Bi deficiency effectively weaken the scattering of electrons from the intrinsic VMg and enhance phonon scattering. A peak zT of 1.82 at 773 K and high conversion efficiency of 11.3% at ∆T = 473 K are achieved in the optimized composition of Mg3 (Sb,Bi)2 by tuning the defect combination. This work demonstrates a feasible and effective approach to improving the performance of Mg3 (Sb,Bi)2 as an emerging thermoelectric material.
GeTe and (Bi,Sb)2Te3 are two representative thermoelectric (TE) materials showing maximum performance at middle and low temperature, respectively. In order to achieve higher performance over the whole temperature range, their segmented one‐leg TE modules are designed and fabricated by one‐step spark plasma sintering (SPS). To search for contact and connect layers, the diffusion behavior of Fe, Ni, Cu, and Ti metal layers in GeTe is studied systematically. The results show that Ti with a similar linear expansivity (10.80 × 10−6 K−1) to GeTe, has low contact resistance (3 µΩ cm2) and thin diffusion layer (0.4 µm), and thus is an effective metallization layer for GeTe. The geometric structure of the GeTe/(Bi,Sb)2Te3 segmented one‐leg TE module and the ratio of GeTe to (Bi,Sb)2Te3 are determined by finite element simulation method. When the GeTe height ratio is 0.66, its theoretical maximum conversion efficiency (ηmax) can reach 15.9% without considering the thermal radiation and thermal/electrical contact resistance. The fabricated GeTe/(Bi,Sb)2Te3 segmented one‐leg TE module showed a ηmax up to 9.5% with a power density ≈ 7.45 mW mm−2, which are relatively high but lower than theoretical predictions, indicating that developing segmented TE modules is an effective approach to enhance TE conversion efficiency.
Abstract Mg3(Sb,Bi)2 is a promising thermoelectric material suited for electronic cooling, but there is still room to optimize its low-temperature performance. This work realizes >200% enhancement in room-temperature zT by incorporating metallic inclusions (Nb or Ta) into the Mg3(Sb,Bi)2-based matrix. The electrical conductivity is boosted in the range of 300–450 K, whereas the corresponding Seebeck coefficients remain unchanged, leading to an exceptionally high room-temperature power factor >30 μW cm−1 K−2; such an unusual effect originates mainly from the modified interfacial barriers. The reduced interfacial barriers are conducive to carrier transport at low and high temperatures. Furthermore, benefiting from the reduced lattice thermal conductivity, a record-high average zT > 1.5 and a maximum zT of 2.04 at 798 K are achieved, resulting in a high thermoelectric conversion efficiency of 15%. This work demonstrates an efficient nanocomposite strategy to enhance the wide-temperature-range thermoelectric performance of n-type Mg3(Sb,Bi)2, broadening their potential for practical applications.
Isobaric specific heat capacity (C-p) is an important parameter not only in physics but also for most materials. Its accurate measurement is particularly critical for performance evaluation of thermoelectric materials, but the experiments by differential scanning calorimetry (DSC) often lead to large uncertainties in the measurements, especially at elevated temperatures. In this study, we propose a simple method to determine C-p by measuring the sound velocity (v) based on lattice vibration and expansion theory. The relative standard error of the v is smaller than 1%, showing good accuracy and repeatability. The calculated C-p at elevated temperature (>300 K) increases slightly with increasing temperature due to the lattice expansion, which is more reasonable than the Dulong-Petit value.
Nanopores with modified surfaces introduced by simultaneously adding BiI3 and Zn significantly improved the ZT value of (Bi,Sb)2Te3.
White-light emission (WLE) materials based on organic-inorganic hybrid lead halides have drawn considerable attention because of their applications in light-emission equipment. Despite considerable efforts, there is still a lack of two-dimensional (2D) lead-chlorine white-light emitting halides with high photoluminescence quantum efficiency (PLQE). Herein, we report the preparation of a new 2D layered hybrid halide, [DTHPE]Pb4Cl10, which exhibits bright wide-band WLE, a high PLQE of 8.86% and high anti-water stability. To the best of our knowledge, the PLQE of [DTHPE]Pb4Cl10 exceeds that of most 2D lead chlorides. Furthermore, the emission intensity is unchanged even after continuous immersion in water for 7 days. Photoluminescence measurements indicate that the WLE originates from self-trapped excitons. [DTHPE]Pb4Cl10 is a promising visible-blind UV hybrid halide owing to its excellent photoelectric response. [DTHPE]Pb4Cl10 is an effective white-light emitting material for display applications. The coexistence of a high performance visible-blind UV response and high efficiency white-light emission provides attractive possibilities for potential applications in the multifunctional photoelectronic field.
Ordinal regression with anchored reference samples (ORARS) has been proposed for predicting the subjective Mean Opinion Score (MOS) of input stimuli automatically. The ORARS addresses the MOS prediction problem by pairing a test sample with each of the pre-scored anchored reference samples. A trained binary classifier is then used to predict which sample, test or anchor, is better statistically. Posteriors of the binary preference decision are then used to predict the MOS of the test sample. In this paper, rigorous framework, analysis, and experiments to demonstrate that ORARS are advantageous over simple regressions are presented. The contributions of this work are: 1) Show that traditional regression can be reformulated into multiple preference tests to yield a better performance, which is confirmed with simulations experimentally; 2) Generalize ORARS to other regression problems and verify its effectiveness; 3) Provide some prerequisite conditions which can insure proper application of ORARS.
An R–P type two-dimensional hybrid perovskite (C 8 H 11 FN) 2 PbBr 4 , which exhibits spectral selective photoresponse for UV light.
GeTe is a promising mid-temperature thermoelectric compound but inevitably contains excessive Ge vacancies hindering its performance maximization. This work reveals that significant enhancement in the dimensionless figure of merit ( ZT ) could be realized by defect structure engineering from point defects to line and plane defects of Ge vacancies. The evolved defects including dislocations and nanodomains enhance phonon scattering to reduce lattice thermal conductivity in GeTe. The accumulation of cationic vacancies toward the formation of dislocations and planar defects weakens the scattering against electronic carriers, securing the carrier mobility and power factor. This synergistic effect on electronic and thermal transport properties remarkably increases the quality factor. As a result, a maximum ZT > 2.3 at 648 K and a record-high average ZT (300-798 K) were obtained for Bi 0.07 Ge 0.90 Te in lead-free GeTe-based compounds. This work demonstrates an important strategy for maximizing the thermoelectric performance of GeTe-based materials by engineering the defect structures, which could also be applied to other thermoelectric materials.