Screw‐Dislocation‐Driven Bidirectional Spiral Growth of Bi2Se3 Nanoplates

Bi₂Se₃ attracts intensive attention as a typical thermoelectric material and a promising topological insulator material. However, previously reported Bi₂Se₃ nanostructures are limited to nanoribbons and smooth nanoplates. Herein, we report the synthesis of spiral Bi₂Se₃ nanoplates and their screw‐dislocation‐driven (SDD) bidirectional growth process. Typical products showed a bipyramid‐like shape with two sets of centrosymmetric helical fringes on the top and bottom faces. Other evidence for the unique structure and growth mode include herringbone contours, spiral arms, and hollow cores. Through the manipulation of kinetic factors, including the precursor concentration, the pH value, and the amount of reductant, we were able to tune the supersaturation in the regime of SDD to layer‐by‐layer growth. Nanoplates with preliminary dislocations were discovered in samples with an appropriate supersaturation value and employed for investigation of the SDD growth process.     

Tuning Optimum Temperature Range of Bi2Te3‐Based Thermoelectric Materials by Defect Engineering

Bi₂Te₃‐based solid solutions, which have been widely used as thermoelectric (TE) materials for the room temperature TE refrigeration, are also the potential candidates for the power generators with medium and low‐temperature heat sources. Therefore, depending on the applications, Bi₂Te₃‐based materials are expected to exhibit excellent TE properties in different temperature ranges. Manipulating the point defects in Bi₂Te₃‐based materials is an effective and important method to realize this purpose. In this review, we focus on how to optimize the TE properties of Bi₂Te₃‐based TE materials in different temperature ranges by defect engineering. Our calculation results of two‐band model revel that tuning the carrier concentration and band gap, which is easily realized by defects engineering, can obtain better TE properties at different temperatures. Then, the typical paradigms about optimizing the TE properties at different temperatures for n‐type and p‐type Bi₂Te₃‐based ZM ingots and polycrystals are discussed in the perspective of defects engineering. This review can provide the guidance to improve the TE properties of Bi₂Te₃‐based materials at different temperatures by defects engineering.     

A New Strategy for Realizing the Conversion of “Homo–Hetero–Homo” Heteroepitaxial Growth in Bi2Te3 and the Thermoelectric Performance

Uncovering the reason for structure‐dependent thermoelectric performance still remains a big challenge. A low‐temperature and easily scalable strategy for synthesizing Bi₂Te₃ nanostring hierarchical structures through solution‐phase reactions, during which there is the conversion of “homo–hetero–homo” in Bi₂Te₃ heteroepitaxial growth, is reported. Bi₂Te₃ nanostrings are obtained through the transformation from pure Bi₂Te₃ hexagonal nanosheets followed by Te?Bi₂Te₃ “nanotop” heterostructures to Bi₂Te₃ nanostrings. The growth of Bi₂Te₃ nanostrings appears to be a self‐assembly process through a wavy competition process generated from Te and Bi³⁺. The conversion of homo–hetero–homo opens up new platforms to investigate the wet chemistry of Bi₂Te₃ nanomaterials. Furthermore, to study the effect of morphologies and hetero/homo structures, especially with the same origin and uniform conditions on their thermoelectric properties, the thermoelectric properties of Bi₂Te₃ nanostrings and Te?Bi₂Te₃ heterostructured pellets fabricated by spark plasma sintering have been investigated separately.     

The Influence of Nanoscale Heterostructures on the Thermoelectric Properties of Bi‐substituted Tl5Te3

Tl_4.5Bi_0.5Te₃ crystallizes in a distorted variant of the Tl₅Te₃ structure type in the space group I4/m. The symmetry reduction compared to Tl₅Te₃ (space group I4/mcm) is a consequence of cation ordering as shown by resonant X‐ray scattering using synchrotron radiation. Tl and Bi predominantly occupy one Wyckoff site each. This ordering is accompanied by displacements of Te atoms. The influence of nanostructuring on the thermoelectric performance of Tl_4.5Bi_0.5Te₃ was investigated for the new composite model system Tl_4.5Bi_0.5Te₃ – TlInTe₂. For the nominal composition (Tl_4.5Bi_0.5Te₃)_0.6(TlInTe₂)_0.4, the thermoelectric Figure of merit ZT reaches 0.8 at 325 °C. Nanoscaled precipitates with sizes of about 100–200 nm probably have beneficial influence on the thermal conductivity at this temperature.     

Synthetic Nanosheets of Natural van der Waals Heterostructures

Creation of new van der Waals heterostructures by stacking different two dimensional (2D) crystals on top of each other in a chosen sequence is the next challenge after the discovery of graphene, mono/few layer of h ‐BN, and transition‐metal dichalcogenides. However, chemical syntheses of van der Waals heterostructures are rarer than the physical preparation techniques. Herein, we demonstrate the kinetic stabilization of 2D ultrathin heterostructure (ca. 1.13–2.35 nm thick) nanosheets of layered intergrowth SnBi₂Te₄, SnBi₄Te₇, and SnBi₆Te₁₀, which belong to the Sn_m Bi_2n Te_{3n +m} homologous series, by a simple solution based synthesis. Few‐layer nanosheets exhibit ultralow lattice thermal conductivity (κ _lat) of 0.3–0.5 W m⁻¹ K⁻¹ and semiconducting electron‐transport properties with high carrier mobility.     

Facile Synthesis and Thermoelectric Properties of Self‐assembled Bi2Te3 One‐Dimensional Nanorod Bundles

Self‐assembled Bi₂Te₃ one‐dimensional nanorod bundles have been fabricated by a low‐cost and facile solvothermal method with ethylene diamine tetraacetic acid as an additive. The phase structures and morphologies of the samples were characterized by X‐ray diffraction, scanning electron microscopy, Fourier‐transform infrared spectrometry, and transmission electron microscope measurements. The growth mechanisms have been proposed based on the experimental results. The full thermoelectric properties of the nanorod bundles have been characterized and show a large improvement in the thermal conductivity attributed to phonon scattering of the nanostructures and then enhance the thermoelectric figure of merit. This work is promising for the realization of new types of highly efficient thermoelectric semiconductors by this method.     

Characterisation of electroplated Bi<Subscript>2</Subscript>(Te<Subscript>1−x</Subscript>Se<Subscript>x</Subscript>)<Subscript>3</Subscript> alloys

Composition modulated Bi₂(Te_1−xSe_x)₃ thin films were prepared on stainless steel substrates by cathodic electrodeposition. The composition was dependent on the deposition conditions. It was possible to obtain, in the same electrolyte, films with either an excess or a deficiency of bismuth in relation to stoichiometric Bi₂(Te_0.9Se_0.1)₃ by changing the deposition potential or the applied current density. The excess of bismuth was reached at the highest cathodic conditions. The variation of the crystallographic axis and the morphology with a granular structure were correlated with the presence of the Bi enrichment in the ternary. The crystallographic texture of bismuth telluride films was studied according to the electrodeposition conditions. The films presented a fibre texture, and a main orientation {11.0} was observed. Electrical and thermoelectric properties of a Bi_1.98Te_2.67Se_0.39 film were measured and showed an n-type behaviour.     

Intrinsically Low Thermal Conductivity and High Carrier Mobility in Dual Topological Quantum Material,n-Type BiTe

A challenge in thermoelectrics is to achieve intrinsically low thermal conductivity in crystalline solids while maintaining a high carrier mobility (μ). Topological quantum materials, such as the topological insulator (TI) or topological crystalline insulator (TCI) can exhibit high μ. Weak topological insulators (WTI) are of interest because of their layered hetero-structural nature which has a low lattice thermal conductivity (κ_lat). BiTe, a unique member of the (Bi₂)_m(Bi₂Te₃)_n homologous series (m:n=1:2), has both the quantum states, TCI and WTI, which is distinct from the conventional strong TI, Bi₂Te₃ (where m:n=0:1). Herein, we report intrinsically low κ_lat of 0.47–0.8 W m⁻¹ K⁻¹ in the 300–650 K range in BiTe resulting from low energy optical phonon branches which originate primarily from the localized vibrations of Bi bilayer. It has high μ≈516 cm² V⁻¹ s⁻¹ and 707 cm² V⁻¹ s⁻¹ along parallel and perpendicular to the spark plasma sintering (SPS) directions, respectively, at room temperature.     

Creating Zipper‐Like van der Waals Gap Discontinuity in Low‐Temperature‐Processed Nanostructured PbBi2nTe1+3n: Enhanced Phonon Scattering and Improved Thermoelectric Performance

Nanoengineered materials can embody distinct atomic structures which deviate from that of the bulk‐grain counterpart and induce significantly modified electronic structures and physical/chemical properties. The phonon structure and thermal properties, which can also be potentially modulated by the modified atomic structure in nanostructured materials, however, are seldom investigated. Employed here is a mild approach to fabricate nanostructured PbBi_2nTe_1+3n using a solution‐synthesized PbTe‐Bi₂Te₃ nano‐heterostructure as a precursor. The as‐obtained monoliths have unprecedented atomic structure, differing from that of the bulk counterpart, especially the zipper‐like van der Waals gap discontinuity and the random arrangement of septuple‐quintuple layers. These structural motifs break the lattice periodicity and coherence of phonon transport, leading to ultralow thermal conductivity and excellent thermoelectric z T.     

Room-Temperature High-Performance Thermoelectric Bi0.6Sb0.4Te: Elimination of Detrimental Band Inversion in BiTe

Room-temperature thermoelectric materials are the key to miniaturizing refrigeration equipment and have great scientific and social implications, yet their application is hindered by their extreme scarcity. BiTe exhibiting strong spin-orbit coupling peaks ZT at 600 K. Herein, we discover the synergy effect of Sb doping in BiTe that eliminates the detrimental band inversion and leads to an overlap of conduction band (CB) and valence band that significantly increases the S from 33 to 124 μV K⁻¹. In addition, this effect enhances the μ from 58 to 92 cm² V⁻¹ s⁻¹ owing to the sharp increase in the CB slope along the Γ-A in the first Brillouin zone. Furthermore, Sb doping increases the anharmonicity, shortens the phonon lifetime and lowers κ_lat. Finally, Se/Sb codoping further optimizes the ZT to 0.6 at 300 K, suggesting that Bi_0.6Sb_0.4Te_1−ySe_y is a potential room-temperature TE material.     

l‐Methioninium chloride and l‐seleno­methioninium chloride at 103 K

The crystal structures of the title compounds, (S)‐1‐carboxy‐3‐(methyl­sulfanyl)­propanaminium chloride, C₅H₁₂NO₂S⁺·Cl⁻, and (S)‐1‐carboxy‐3‐(methyl­selanyl)­propanaminium chloride, C₅H₁₂NO₂Se⁺·Cl⁻, are isomorphous. The proton­ated l ‐methionine and l ‐seleno­methionine mol­ecules have almost identical conformations and create very similar contacts with the Cl⁻ anions in the crystal structures of both compounds. The amino acid cations and the Cl⁻ anions are linked viaN—H⋯Cl⁻ and O—H⋯Cl⁻ hydrogen bonds.     

Modulating the thermoelectric transport properties of the novel material Er2Te3 via strain

The rare-earth chalcogenide Er₂Te₃, characterized by its low lattice thermal conductivity, represents a highly promising and innovative thermoelectric material. However, there have been limited studies exploring its thermoelectric properties in depth. Additionally, it has been discovered that strain engineering is an effective method for enhancing thermoelectric properties, a technique successfully applied to relevant materials. In this study, we employed a first-principles approach in conjunction with the semi-classical Boltzmann transport theory to investigate the thermoelectric properties of Er₂Te₃ materials under −4% to 4% strain. The results indicate that applying compressive strain modulates thermoelectric properties more effectively than tensile strain for Er₂Te₃. Under strain modulation, the maximum power factor for both p-type and n-type Er₂Te₃ increases significantly, from 0.9 to 2.5 mW m⁻¹ K⁻² and from 14 to 18 mW m⁻¹ K⁻² at 300 K, respectively. Moreover, the figure of merit (ZT) for p-type and n-type Er₂Te₃ improves notably, from 0.15 to 0.25 and from 1.15 to 1.35, respectively, under −4% strain. Consequently, the thermoelectric properties of Er₂Te₃ materials can be significantly enhanced through strain application, with n-type Er₂Te₃ demonstrating substantial potential as a thermoelectric material.     

微波加热制备空心和锯齿形貌Bi_2Te_3晶体(英文)

Well-crystallized Bi₂Te₃ hollow spheres and nanosaws were prepared by microwave heating. Both the ionic liquid and the microwave heating play important role in the formation of the above nanostructures. Hollow spheres can not be obtained only by electronic stove heating, while the addition of ionic liquid leads to fast preparation of nanosaws structure under microwave heating conditions. The similar experimental results have been observed in the preparation of Bi₂S₃, Sb₂S₃ and Bi₂Se₃ nanostructures.     

Selen‐Polykationen stabilisiert durch polymere Chlorobismutat‐Anionen: Synthesen und Kristallstrukturen von Se4[Bi4Cl14] und Se10[Bi5Cl17]

Selenium Polycations Stabilized by Polymeric Chlorobismuthate Anions: Syntheses and Crystal Structures of Se₄[Bi₄Cl₁₄] and Se₁₀[Bi₅Cl₁₇] Reactions of selenium with selenium(IV) chloride and bismuth(III) chloride in sealed evacuated glass ampoules at temperatures between 110 and 155 °C yield a series of compounds which are composed of discrete selenium polycations and polymeric chlorobismutate anions. Besides the already known Se₈[Bi₄Cl₁₄] two new compounds have been identified by crystal structure analyses as Se₄[Bi₄Cl₁₄] (tetragonal, P4/n, a = 1089.1(2) pm, c = 993.7(2) pm, Z = 2) and Se₁₀[Bi₅Cl₁₇] (monoclinic, P2₁/c, a = 1079.24(8) pm, b = 2062.9(2) pm, c = 1676.1(2) pm, β = 90.87(1)°, Z = 4). Se₄[Bi₄Cl₁₄] was obtained as red transparent platelike crystals and is the first example of a compound with (chalcogen₄)²⁺ ions of exact square‐planar symmetry and molecular point group D_4h in the solid state. The cations are surrounded by layers of two‐dimensional polymeric anions [Bi₄Cl₁₄]^2–. Se₁₀[Bi₅Cl₁₇] forms dark grey crystals with a reddish luster. The structure contains the known bicyclic polycation Se₁₀²⁺ which is disordered over two positions and the first three‐dimensional polymeric chlorobismutate anion [Bi₅Cl₁₇]^2–. The different BiCl_x polyhedra are linked by sharing common vertices, edges, and faces.     

A square‐planar tellurium(II) complex with Te,Te′‐chelating ligands

While exploring the chemistry of tellurium‐containing dichalcogenidoimidodiphosphinate ligands, the first all‐tellurium member of a series of related square‐planar E^II(E′)₄ complexes (E and E′ are group 16 elements), namely bis(P,P,P′,P′‐tetraphenylditelluridoimidodiphosphinato‐κ²Te,Te′)tellurium(II) (systematic name: 2,2,4,4,8,8,10,10‐octaphenyl‐1λ³,5,6λ⁴,7λ³,11‐pentatellura‐3,9‐diaza‐2λ⁵,4λ⁵,8λ⁵,10λ⁵‐tetraphosphaspiro[5.5]undeca‐1,3,7,9‐tetraene), C₄₈H₄₀N₂P₄Te₅, was obtained unexpectedly. The formally Te^II centre is situated on a crystallographic inversion centre and is Te,Te′‐chelated to two anionic [(TePPh₂)₂N]⁻ ligands in an anti conformation. The central Te^II(Te)₄ unit is approximately square planar [Te—Te—Te = 93.51 (3) and 86.49 (3)°], with Te—Te bond lengths of 2.9806 (6) and 2.9978 (9) Å.     

Intrinsically Low Thermal Conductivity and High Carrier Mobility in Dual Topological Quantum Material,n‐Type BiTe

A challenge in thermoelectrics is to achieve intrinsically low thermal conductivity in crystalline solids while maintaining a high carrier mobility (μ). Topological quantum materials, such as the topological insulator (TI) or topological crystalline insulator (TCI) can exhibit high μ. Weak topological insulators (WTI) are of interest because of their layered hetero‐structural nature which has a low lattice thermal conductivity (κ_lat). BiTe, a unique member of the (Bi₂)_m(Bi₂Te₃)_n homologous series (m:n=1:2), has both the quantum states, TCI and WTI, which is distinct from the conventional strong TI, Bi₂Te₃ (where m:n=0:1). Herein, we report intrinsically low κ_lat of 0.47–0.8 W m^?1 K^?1 in the 300–650 K range in BiTe resulting from low energy optical phonon branches which originate primarily from the localized vibrations of Bi bilayer. It has high μ≈516 cm² V^?1 s^?1 and 707 cm² V^?1 s^?1 along parallel and perpendicular to the spark plasma sintering (SPS) directions, respectively, at room temperature.     

Thermoelectric properties of Cu-doped n-type (Bi2Te3)0.9–(Bi2−xCuxSe3)0.1(x=0–0.2) alloys

n-Type (Bi₂Te₃)_0.9–(Bi_2−xCu_xSe₃)_0.1 (x=0–0.2) alloys with Cu substitution for Bi were prepared by spark plasma-sintering technique and their structural and thermoelectric properties were evaluated. Rietveld analysis reveals that approximate 9.0% of Bi atomic sites are occupied by Cu atoms and less than 4.0 wt% second phase Cu_2.86Te₂ precipitated in the Cu-doped parent alloys. Measurements show that an introduction of a small amount of Cu (x0.1) can reduce the lattice thermal conductivity (κ_L), and improve the electrical conductivity and Seebeck coefficient. An optimal dimensionless figure of merit (ZT) value of 0.98 is obtained for x=0.1 at 417 K, which is obviously higher than those of Cu-free Bi₂Se_0.3Te_2.7 (ZT=0.66) and Ag-doped alloys (ZT=0.86) prepared by the same technologies.     

Heavy Chalcogenide-Based Ionic Liquids in Syntheses of Metal Chalcogenide Materials near Room Temperature

This minireview describes two strategically different and unexplored approaches to use ionic liquids (IL) containing weakly solvated and highly reactive chalcogenide anions [E-SiMe₃]⁻ and [E−H]⁻ of the heavy chalcogens (E=S, Se, Te) in materials synthesis near room temperature. The first strategy involves the synthesis of unprecedented trimethylsilyl chalcogenido metalates Cat⁺[M(E-SiMe₃)_n]⁻ (Cat=organic IL cation) of main group and transition metals (M=Ga, In, Sn, Zn, Cu, Ag, Au). These fully characterized homoleptic metalates serve as thermally metastable precursors in low-temperature syntheses of binary, ternary and even quaternary chalcogenide materials such as CIGS and CZTS relevant for semiconductor and photovoltaics (PV) applications. Furthermore, thermally and protolytically metastable coinage metalates Cat⁺[M(ESiMe₃)₂]⁻ (M=Cu, Ag, Au; E=S, Se) are accessible. Finally, the use of precursors BMPyr[E-SiMe₃] (E=Se,Te; BMPyr=1-butyl-1-methylpyrrolidinium) as sources of activated selenium and tellurium in the synthesis of high-grade thermoelectric nanoparticles Bi₂Se₃ and Bi₂Te₃ is shortly highlighted. The second synthesis strategy involves the metalation of ionic liquids Cat[S−H] and Cat[Se−H] by protolytically highly active metal alkyls or amides R_nM. This rather general approach towards unknown chalcogenido metalates Cat_m[R_n-1M(E)]_m (E=S, Se) will be demonstrated in a research paper following this short review head-to-tail.     

Ordnungsvarianten in ternären Chalkogeniden mit aufgefüllter β‐Manganstruktur

Ordered Structural Variants in Ternary Chalcogenides with Filled β‐Manganese Structure Ternary chalcogenides with filled β;‐manganese structure show the tendency to form differently ordered structural variants. In the case of AM₆Te₁₀ (A = Ca, Sn, Pb; M = Al, Ga) and A₂M₆Ch₁₀ (Na₂Ga₆Te₁₀, Na₂Ga₆Se₁₀ and the new compound Na₂In₆Se₁₀) there are different prerequisites for the formation of ordered variants. High resolution transmission electron microscopy (HRTEM) and electron diffraction performed on AM₆Te₁₀ give evidence of different distributions of the cations in the metaprismatic cavities of apparently homogenous samples. Besides completely ordered domains, crystals with partially ordered structures can be observed. In the case of A₂M₆Ch₁₀, the different structures are exclusively formed by different ordered distributions of M³⁺ in the tetrahedral cavities. This work focuses on the structural variants which can be synthesized by direct substitution of M³⁺. The complex structures can be systematized by using crystallographic group‐subgroup relations. Detailed analyses emphasize the close topological relation of these phases to the aristotype (β;‐manganese) and prove that M³⁺ occupy cavities of the same type (T4 and T5) in all structures.