Room-Temperature Synthesis and Low Thermal Conductivity in Nanocrystalline Ag3CuS2.

Noble-metal-based chalcogenide materials recently gained massive attention in the field of thermoelectrics. In most cases, materials are synthesized using (i) high-temperature solid-state reactions or (ii) soft chemical methods where temperature requirements are lower than those of solid-state reactions (generally below 400 °C). Herein, we present a simple, surfactant-free, room-temperature, and energy-efficient synthesis of Ag3CuS2 nanocrystals. The present synthesis technique is scalable and capable of gram-scale production. A spark plasma sintering (SPS) pressed sample exhibits ultralow thermal conductivity (∼0.31 W/mK at room temperature). We found that Ag3CuS2 exhibits low sound velocity, as well as a non-Debye-like behavior based on a low-temperature heat capacity measurement. A high degree of anharmonicity of bonding, soft vibrations modes, and nanoscale grain boundary scattering in Ag3CuS2 lead to ultralow thermal conductivity, which can be important for thermoelectrics, optoelectronics, and thermal barrier coating applications.

Anomalous Hall Conductivity and Nernst Effect of the Ideal Weyl Semimetallic Ferromagnet EuCd2 As2.

Weyl semimetal is a unique topological phase with topologically protected band crossings in the bulk and robust surface states called Fermi arcs. Weyl nodes always appear in pairs with opposite chiralities, and they need to have either time-reversal or inversion symmetry broken. When the time-reversal symmetry is broken the minimum number of Weyl points (WPs) is two. If these WPs are located at the Fermi level, they form an ideal Weyl semimetal (WSM). In this study, intrinsic ferromagnetic (FM) EuCd2 As2 are grown, predicted to be an ideal WSM and studied its electronic structure by angle-resolved photoemission spectroscopy, and scanning tunneling microscopy which agrees closely with the first principles calculations. Moreover, anomalous Hall conductivity and Nernst effect are observed, resulting from the non-zero Berry curvature, and the topological Hall effect arising from changes in the band structure caused by spin canting produced by magnetic fields. These findings can help realize several exotic quantum phenomena in inorganic topological materials that are otherwise difficult to assess because of the presence of multiple pairs of Weyl nodes.

Large Room Temperature Anomalous Transverse Thermoelectric Effect in Kagome Antiferromagnet YMn6 Sn6.

Kagome magnets possess several novel nontrivial topological features owing to the strong correlation between topology and magnetism that extends to their applications in the field of thermoelectricity. Conventional thermoelectric (TE) devices use the Seebeck effect to convert heat into electrical energy. In contrast, transverse thermoelectric devices based on the Nernst effect are attracting recent attention due to their unique transverse geometry, which uses a single material to eliminate the need for a multitude of electrical connections compared to conventional TE devices. Here, a large anomalous transverse thermoelectric effect of ≈2 µV K-1 at room temperature in a kagome antiferromagnet YMn6 Sn6 single crystal is obtained. The obtained value is larger than that of state-of-the-art canted antiferromagnetic (AFM) materials and comparable with ferromagnetic systems. The large anomalous Nernst effect (ANE) can be attributed to the net Berry curvature near the Fermi level. Furthermore, the ANE of the AFM YMn6 Sn6 exceeds the magnetization scaling relationship of conventional ferromagnets. The results clearly illustrate that AFM material YMn6 Sn6 is an ideal topological material for room-temperature transverse thermoelectric applications.

Giant Topological Hall Effect in the Noncollinear Phase of Two-Dimensional Antiferromagnetic Topological Insulator MnBi4Te7.

Magnetic topological insulators provide an important platform for realizing several exotic quantum phenomena, such as the axion insulating state and the quantum anomalous Hall effect, owing to the interplay between topology and magnetism. MnBi4Te7 is a two-dimensional Z2 antiferromagnetic (AFM) topological insulator with a Néel temperature of ∼13 K. In AFM materials, the topological Hall effect (THE) is observed owing to the existence of nontrivial spin structures. A material with noncollinearity that develops in the AFM phase rather than at the onset of the AFM order is particularly important. In this study, we observed that such an unanticipated THE starts to develop in a MnBi4Te7 single crystal when the magnetic field is rotated away from the easy axis (c-axis) of the system. Furthermore, the THE resistivity reaches a giant value of ∼7 µΩ-cm at 2 K when the angle between the magnetic field and the c-axis is 75°. This value is significantly higher than the values for previously reported systems with noncoplanar structures. The THE can be ascribed to the noncoplanar spin structure resulting from the canted state during the spin-flip transition in the ground AFM state of MnBi4Te7. The large THE at a relatively low applied field makes the MnBi4Te7 system a potential candidate for spintronic applications.

Large Anomalous Hall and Nernst Effects in High Curie-Temperature Iron-Based Heusler Compounds.

The interplay between topology and magnetism has recently sparked the frontier studies of magnetic topological materials that exhibit intriguing anomalous Hall and Nernst effects owning to the large intrinsic Berry curvature (BC). To better understand the anomalous quantum transport properties of these materials and their implications for future applications such as electronic and thermoelectric devices, it is crucial to discover more novel material platforms for performing anomalous transverse transport studies. Here, it is experimentally demonstrated that low-cost Fe-based Heusler compounds exhibit large anomalous Hall and Nernst effects. An anomalous Hall conductivity of 250-750 S cm-1 and Nernst thermopower of above 2 µV K-1 are observed near room temperature. The positive effect of anti-site disorder on the anomalous Hall transport is revealed. Considering the very high Curie temperature (nearly 1000 K), larger Nernst thermopowers at high temperatures are expected owing to the existing magnetic order and the intrinsic BC. This work provides a background for developing low-cost Fe-based Heusler compounds as a new material platform for anomalous transport studies and applications, in particular, near and above room temperature.

2D-Berry-Curvature-Driven Large Anomalous Hall Effect in Layered Topological Nodal-Line MnAlGe.

Topological magnets comprising 2D magnetic layers with Curie temperatures (TC ) exceeding room temperature are key for dissipationless quantum transport devices. However, the identification of a material with 2D ferromagnetic planes that exhibits an out-of-plane-magnetization remains a challenge. This study reports a ferromagnetic, topological, nodal-line, and semimetal MnAlGe composed of square-net Mn layers that are separated by nonmagnetic Al-Ge spacers. The 2D ferromagnetic Mn layers exhibit an out-of-plane magnetization below TC  ≈ 503 K. Density functional calculations demonstrate that 2D arrays of Mn atoms control the electrical, magnetic, and therefore topological properties in MnAlGe. The unique 2D distribution of the Berry curvature resembles the 2D Fermi surface of the bands that form the topological nodal line near the Fermi energy. A large anomalous Hall conductivity of ≈700 S cm-1 is obtained at 2 K and related to this nodal-line-induced 2D Berry curvature distribution. The high transition temperature, large anisotropic out-of-plane magnetism, and natural heterostructure-type atomic arrangements consisting of magnetic Mn and nonmagnetic Al/Ge elements render nodal-line MnAlGe one of the few, unique, and layered topological ferromagnets that have ever been observed.

Topological Quantum Materials from the Viewpoint of Chemistry.

Topology, a mathematical concept, has recently become a popular and truly transdisciplinary topic encompassing condensed matter physics, solid state chemistry, and materials science. Since there is a direct connection between real space, namely atoms, valence electrons, bonds, and orbitals, and reciprocal space, namely bands and Fermi surfaces, via symmetry and topology, classifying topological materials within a single-particle picture is possible. Currently, most materials are classified as trivial insulators, semimetals, and metals or as topological insulators, Dirac and Weyl nodal-line semimetals, and topological metals. The key ingredients for topology are certain symmetries, the inert pair effect of the outer electrons leading to inversion of the conduction and valence bands, and spin-orbit coupling. This review presents the topological concepts related to solids from the viewpoint of a solid-state chemist, summarizes techniques for growing single crystals, and describes basic physical property measurement techniques to characterize topological materials beyond their structure and provide examples of such materials. Finally, a brief outlook on the impact of topology in other areas of chemistry is provided at the end of the article.

Largely Suppressed Magneto-Thermal Conductivity and Enhanced Magneto-Thermoelectric Properties in PtSn4.

Highly conductive topological semimetals with exotic electronic structures offer fertile ground for the investigation of the electrical and thermal transport behavior of quasiparticles. Here, we find that the layer-structured Dirac semimetal PtSn4 exhibits a largely suppressed thermal conductivity under a magnetic field. At low temperatures, a dramatic decrease in the thermal conductivity of PtSn4 by more than two orders of magnitude is obtained at 9 T. Moreover, PtSn4 shows both strong longitudinal and transverse thermoelectric responses under a magnetic field. Large power factor and Nernst power factor of approximately 80-100 µW·cm-1·K-2 are obtained around 15 K in various magnetic fields. As a result, the thermoelectric figure of merit zT is strongly enhanced by more than 30 times, compared to that without a magnetic field. This work provides a paradigm for the decoupling of the electron and hole transport behavior of highly conductive topological semimetals and is helpful for developing topological semimetals for thermoelectric energy conversion.

Observation of giant spin-split Fermi-arc with maximal Chern number in the chiral topological semimetal PtGa.

Non-symmorphic chiral topological crystals host exotic multifold fermions, and their associated Fermi arcs helically wrap around and expand throughout the Brillouin zone between the high-symmetry center and surface-corner momenta. However, Fermi-arc splitting and realization of the theoretically proposed maximal Chern number rely heavily on the spin-orbit coupling (SOC) strength. In the present work, we investigate the topological states of a new chiral crystal, PtGa, which has the strongest SOC among all chiral crystals reported to date. With a comprehensive investigation using high-resolution angle-resolved photoemission spectroscopy, quantum-oscillation measurements, and state-of-the-art ab initio calculations, we report a giant SOC-induced splitting of both Fermi arcs and bulk states. Consequently, this study experimentally confirms the realization of a maximal Chern number equal to ±4 in multifold fermionic systems, thereby providing a platform to observe large-quantized photogalvanic currents in optical experiments.

Intrinsic Anomalous Hall Effect in Ni-Substituted Magnetic Weyl Semimetal Co3Sn2S2.

Topological Weyl semimetals have recently attracted considerable attention among materials scientists as their properties are predicted to be protected against perturbations such as lattice distortion and chemical substitution. However, any experimental proof of such robustness is still lacking. In this study, we experimentally demonstrate that the topological properties of the ferromagnetic kagomé compound Co3Sn2S2 are preserved upon Ni substitution. We systematically vary the Ni content in Co3Sn2S2 single crystals and study their magnetic and anomalous transport properties. For the intermediate Ni substitution, we observe a remarkable increase in the coercive field while still maintaining significant anomalous Hall conductivity. The large anomalous Hall conductivity of these compounds is intrinsic, consistent with first-principles calculations, which proves its topological origin. Our results can guide further studies on the chemical tuning of topological materials for better understanding.

Extremely high conductivity observed in the triple point topological metal MoP.

Weyl and Dirac fermions have created much attention in condensed matter physics and materials science. Recently, several additional distinct types of fermions have been predicted. Here, we report ultra-high electrical conductivity in MoP at low temperature, which has recently been established as a triple point fermion material. We show that the electrical resistivity is 6 nΩ cm at 2 K with a large mean free path of 11 microns. de Haas-van Alphen oscillations reveal spin splitting of the Fermi surfaces. In contrast to noble metals with similar conductivity and number of carriers, the magnetoresistance in MoP does not saturate up to 9 T at 2 K. Interestingly, the momentum relaxing time of the electrons is found to be more than 15 times larger than the quantum coherence time. This difference between the scattering scales shows that momentum conserving scattering dominates in MoP at low temperatures.

Zero-Field Nernst Effect in a Ferromagnetic Kagome-Lattice Weyl-Semimetal Co3 Sn2 S2.

The discovery of magnetic topological semimetals has recently attracted significant attention in the field of topology and thermoelectrics. In a thermoelectric device based on the Nernst geometry, an external magnet is required as an integral part. Reported is a zero-field Nernst effect in a newly discovered hard-ferromagnetic kagome-lattice Weyl-semimetal Co3 Sn2 S2 . A maximum Nernst thermopower of ≈3 µV K-1 at 80 K in zero field is achieved in this magnetic Weyl-semimetal. The results demonstrate the possibility of application of topological hard magnetic semimetals for low-power thermoelectric devices based on the Nernst effect and are thus valuable for the comprehensive understanding of transport properties in this class of materials.

Soft Phonon Modes Leading to Ultralow Thermal Conductivity and High Thermoelectric Performance in AgCuTe.

Crystalline solids with intrinsically low lattice thermal conductivity (κL ) are crucial to realizing high-performance thermoelectric (TE) materials. Herein, we show an ultralow κL of 0.35 Wm-1 K-1 in AgCuTe, which has a remarkable TE figure-of-merit, zT of 1.6 at 670 K when alloyed with 10 mol % Se. First-principles DFT calculation reveals several soft phonon modes in its room-temperature hexagonal phase, which are also evident from low-temperature heat-capacity measurement. These phonon modes, dominated by Ag vibrations, soften further with temperature giving a dynamic cation disorder and driving the superionic transition. Intrinsic factors cause an ultralow κL in the room-temperature hexagonal phase, while the dynamic disorder of Ag/Cu cations leads to reduced phonon frequencies and mean free paths in the high-temperature rocksalt phase. Despite the cation disorder at elevated temperatures, the crystalline conduits of the rigid anion sublattice give a high power factor.

Origin of the Order-Disorder Transition and the Associated Anomalous Change of Thermopower in AgBiS2 Nanocrystals: A Combined Experimental and Theoretical Study.

Bulk AgBiS2 crystallizes in a trigonal crystal structure (space group, P3̅m1) at room temperature, which transforms to a cation disordered rock salt structure (space group, Fm3̅m) at ∼473 K. Surprisingly, at room temperature, a solution-grown nanocrystal of AgBiS2 crystallizes in a metastable Ag/Bi ordered cubic structure, which transforms to a thermodynamically stable disorded cubic structure at 610 K. Moreover, the order-disorder transition in nanocrystalline AgBiS2 is associated with an unusual change in thermopower. Here, we shed light on the origin of a order-disorder phase transition and the associated anomalous change of thermopower in AgBiS2 nanocrystals by using a combined experimental, density functional theory based first-principles calculation and ab initio molecular dynamics simulations. Positron-annilation spectroscopy indicates the presence of higher numbers of Ag vacancies in the nanocrystal compared to that of the bulk cubic counterpart at room temperature. Furthermore, temperature-dependent two-detector coincidence Doppler broadening spectroscopy and Doppler broadening of the annihilation radiation (S parameter) indicate that the Ag vacancy concentration increases abruptly during the order-disorder transition in nanocrystalline AgBiS2. At high temperature, a Ag atom shuttles between the vacancy and interstitial sites to form a locally disordered cation sublattice in the nanocrystal, which is facilitated by the formation of more Ag vacancies during the phase transition. This process increases the entropy of the system at higher vacancy concentration, which, in turn, results in the unusual rise in thermopower.

The effect of order-disorder phase transitions and band gap evolution on the thermoelectric properties of AgCuS nanocrystals.

Copper and silver based chalcogenides, chalco-halides, and halides form a unique class of semiconductors, as they display mixed ionic and electronic conduction in their superionic phase. These compounds are composed of softly coupled cationic and anionic substructures, and undergo a transition to a superionic phase displaying changes in the substructure of their mobile ions with varying temperature. Here, we demonstrate a facile, ambient and capping agent free solution based synthesis of AgCuS nanocrystals and their temperature dependent (300-550 K) thermoelectric properties. AgCuS is known to show fascinating p-n-p type conduction switching in its bulk polycrystalline form. Temperature dependent synchrotron powder X-ray diffraction, heat capacity and Raman spectroscopy measurements indicate the observation of two superionic phase transitions, from a room temperature ordered orthorhombic (ß) to a partially disordered hexagonal (α) phase at ∼365 K and from the hexagonal (α) to a fully disordered cubic (δ) phase at ∼439 K, in nanocrystalline AgCuS. The size reduction to the nanoscale resulted in a large variation in the thermoelectric properties compared to its bulk counterpart. Temperature dependent Seebeck coefficient measurements indicate that the nanocrystalline AgCuS does not display the p-n-p type conduction switching property like its bulk form, but remains p-type throughout the measured temperature range due to the presence of excess localized Ag vacancies. Nanocrystalline AgCuS exhibits a wider electronic band gap (∼1.2 eV) compared to that of the bulk AgCuS (∼0.9 eV), which is not sufficient to close the band gap to form a semimetallic intermediate state during the orthorhombic to hexagonal superionic phase transition, thus AgCuS nanocrystals do not show conduction type switching properties like their bulk counterpart. The present study demonstrates that ambient solution phase synthesis and size reduction to the nanoscale can tailor the order-disorder phase transition, the band gap and the electronic conduction properties in superionic compounds, which will not only enrich solid-state inorganic chemistry but also open a new avenue to design multifunctional materials.

Temperature driven p-n-p type conduction switching materials: current trends and future directions.

Modern technological inventions have been going through a "renaissance" period. Development of new materials and understanding of fundamental structure-property correlations are the important steps to move further for advanced technologies. In modern technologies, inorganic semiconductors are the leading materials which are extensively used for different applications. In the current perspective, we present discussion on an important class of materials that show fascinating p-n-p type conduction switching, which can have potential applications in diodes or transistor devices that operate reversibly upon temperature or voltage change. We highlight the key concepts, present the current fundamental understanding and show the latest developments in the field of p-n-p type conduction switching. Finally, we point out the major challenges and opportunities in this field.

Temperature dependent reversible p-n-p type conduction switching with colossal change in thermopower of semiconducting AgCuS.

Semiconductors have been fundamental to various devices that are typically operated with electric field, such as transistors, memories, sensors, and resistive switches. There is growing interest in the development of novel inorganic materials for use in transistors and semiconductor switches, which can be operated with a temperature gradient. Here, we show that a crystalline semiconducting noble metal sulfide, AgCuS, exhibits a sharp temperature dependent reversible p-n-p type conduction switching, along with a colossal change in the thermopower (ΔS of ~1757 µV K(-1)) at the superionic phase transition (T of ~364 K). In addition, its thermal conductivity is ultralow in 300-550 K range giving AgCuS the ability to maintain temperature gradients. We have developed fundamental understanding of the phase transition and p-n-p type conduction switching in AgCuS through temperature dependent synchrotron powder X-ray diffraction, heat capacity, Raman spectroscopy, and positron annihilation spectroscopy measurements. Using first-principles calculations, we show that this rare combination of properties originates from an effective decoupling of electrical conduction and phonon transport associated with electronic states of the rigid sulfur sublattice and soft vibrations of the disordered cation sublattices, respectively. Temperature dependent p-n-p type conduction switching makes AgCuS an ideal material for diode or transistor devices that operate reversibly on temperature or voltage changes near room temperature.

Ultrathin septuple layered PbBi2Se4 nanosheets.

Layered lead bismuth selenide, PbBi2Se4, an intergrowth compound of PbSe (rocksalt) and Bi2Se3 (hexagonal), is a topological insulator in the bulk phase. We present a simple solution based synthesis of two dimensional (2D) few seven atomic (septuple) layered PbBi2Se4 nanosheets (4-7 nm thick) for the first time. The excellent electrical transport in ultrathin PbBi2Se4 is attributed to the presence of dominant surface states that offer high electrical mobility (∼153 cm(2) V(-1) s(-1)) and scattering resistant carriers. Ultrathin 3-5 SLs PbBi2Se4 shows an n-type semiconducting behaviour with a band gap of ∼0.6 eV, which is confirmed by optical spectroscopy and thermopower measurements.