High Thermoelectric Performance in the Wide Band‐Gap AgGa1‐xTe2 Compounds: Directional Negative Thermal Expansion and Intrinsically Low Thermal Conductivity

A deficiency of Ga in wide band‐gap AgGa_1‐xTe₂ semiconductors (1.2 eV) can be used to optimize the electrical transport properties and reduce the thermal conductivity to achieve ZT > 1 at 873 K. First‐principles density functional theory calculations and a Boson peak observed in the low temperature heat capacity data indicate the presence of strong coupling between optical phonons with low frequency and heat carrying acoustical phonons, resulting in a depressed maximum of Debye frequency in the first Brillouin zone and low phonon velocities. Moreover, the Ag? Te bond lengths and Te? Ag? Te bond angles increase with rising temperature, leading to a significant distortion of the [AgTe₄]^7? tetrahedra, but an almost unmodified [GaTe₄]^5? tetrahedra. This behavior results in lattice expansion in the ab‐plane and contraction along the c‐axis, corresponding to the positive and negative Gruneisen parameters in the phonon spectral calculations. This effect gives rise to the large anharmonic behavior of the lattice. These factors together with the low frequency vibrations of Ag and Te atoms in the structure lead to an ultralow thermal conductivity of 0.18 W m^?1 K^?1 at 873 K.     

Hierarchical Chemical Bonds Contributing to the Intrinsically Low Thermal Conductivity in α‐MgAgSb Thermoelectric Materials

Understanding the lattice dynamics and phonon transport from the perspective of chemical bonds is essential for improving and finding high‐efficiency thermoelectric materials and for many applications. Here, the coexistence of global and local weak chemical bonds is elucidated as the origin of the intrinsically low lattice thermal conductivity of non‐caged structure Nowotny–Juza compound, α‐MgAgSb, which is identified as a new type of promising thermoelectric material in the temperature range of 300–550 K. The global weak bonds of the compound lead to a low sound velocity. The unique three‐centered Mg? Ag? Sb bonds in α‐MgAgSb vibrate locally and induce low‐frequency optical phonons, resulting in “rattling‐like” thermal damping to further reduce the lattice thermal conductivity. The hierarchical chemical bonds originate from the low valence electron count of α‐MgAgSb, with the feature shared by Nowotny–Juza compounds. Low lattice thermal conductivities are therefore highly possible in this series of compounds, which is verified by phonon and bulk modulus calculations on some of the compositions.     

High Thermoelectric Performance in Sulfide‐Type Argyrodites Compound Ag8Sn(S1−xSex)6 Enabled by Ultralow Lattice Thermal Conductivity and Extended Cubic Phase Regime

Argyrodites with a general chemical formula of A₈BC₆ are known for complex phase transitions, ultralow lattice thermal conductivity, and mixed electronic and ionic conduction. The coexistence of ionic conduction and promising thermoelectric performance have recently been reported in selenide and telluride argyrodites, but scarcely in sulfide argyrodites. Here, the thermoelectric properties of Ag₈Sn(S_1?xSe_x)₆ are reported. Specifically, Ag₈SnS₆ exhibits intrinsically ultralow lattice thermal conductivities of 0.61–0.31 W m^?1 K^?1 over the whole temperature range from 32 to 773 K due to distorted local crystal structure, relatively weak chemical bonding, rattler‐like Ag atoms, low‐lying optical modes, and dynamic disorder of Ag ions at high temperatures. Se doping shifts the orthorhombic–cubic phase transition from 457 K at x = 0 to 430 K at x = 0.10, thereby expanding the temperature range of the thermoelectrically favored cubic phase. A figure of merit zT value ≈ 0.80 is achieved at 773 K in Ag₈Sn(S_1?xSe_x)₆ (x = 0.03), the highest zT value reported in sulfide argyrodites. These results fill a knowledge gap of the thermoelectric study of argyrodites and contribute to a comprehensive understanding of the chemical bonding, lattice dynamics, and thermal transport of argyrodites.     

High Thermoelectric Performance in Supersaturated Solid Solutions and Nanostructured n‐Type PbTe–GeTe

Sb‐doped and GeTe‐alloyed n‐type thermoelectric materials that show an excellent figure of merit ZT in the intermediate temperature range (400–800 K) are reported. The synergistic effect of favorable changes to the band structure resulting in high Seebeck coefficient and enhanced phonon scattering by point defects and nanoscale precipitates resulting in reduction of thermal conductivity are demonstrated. The samples can be tuned as single‐phase solid solution (SS) or two‐phase system with nanoscale precipitates (Nano) based on the annealing processes. The GeTe alloying results in band structure modification by widening the bandgap and increasing the density‐of‐states effective mass of PbTe, resulting in significantly enhanced Seebeck coefficients. The nanoscale precipitates can improve the power factor in the low temperature range and further reduce the lattice thermal conductivity (κ_lat). Specifically, the Seebeck coefficient of Pb_0.988Sb_0.012Te–13%GeTe–Nano approaches ?280 µV K^?1 at 673 K with a low κ_lat of 0.56 W m^?1 K^?1 at 573 K. Consequently, a peak ZT value of 1.38 is achieved at 623 K. Moreover, a high average ZT_avg value of ≈1.04 is obtained in the temperature range from 300 to 773 K for n‐type Pb_0.988Sb_0.012Te–13%GeTe–Nano.     

A 0D Lead‐Free Hybrid Crystal with Ultralow Thermal Conductivity

Organic–inorganic hybrid materials are of significant interest owing to their diverse applications ranging from photovoltaics and electronics to catalysis. Control over the organic and inorganic components offers flexibility through tuning their chemical and physical properties. Herein, it is reported that a new organic–inorganic hybrid, [Mn(C₂H₆OS)₆]I₄, with linear tetraiodide anions exhibit an ultralow thermal conductivity of 0.15 ± 0.01 W m^?1 K^?1 at room temperature, which is among the lowest values reported for organic–inorganic hybrid materials. Interestingly, the hybrid compound has a unique 0D structure, which extends into 3D supramolecular frameworks through nonclassical hydrogen bonding. Phonon band structure calculations reveal that low group velocities and localization of vibrational energy underlie the observed ultralow thermal conductivity, which could serve as a general principle to design novel thermal management materials.     

Anisotropic and Ultralow Phonon Thermal Transport in Organic–Inorganic Hybrid Perovskites: Atomistic Insights into Solar Cell Thermal Management and Thermoelectric Energy Conversion Efficiency

Energy‐related functionality and performance of organic–inorganic hybrid perovskites, such as methylammonium lead iodide (MAPbI₃), highly depend on their thermal transport behavior. Using equilibrium molecular dynamics simulations, it is discovered that the thermal conductivities of MAPbI₃ under different phases (cubic, tetragonal, and orthorhombic) are less than 1 W m^?1 K^?1, and as low as 0.31 W m^?1 K^?1 at room temperature. Such ultralow thermal conductivity can be attributed to the small phonon group velocities due to their low elastic stiffness, in addition to their short phonon lifetimes (<100 ps) and mean‐free‐paths (<10 nm) due to the enhanced phonon–phonon scattering from highly‐overlapped phonon branches. The anisotropy in thermal conductivity at lower temperatures is found to associate with preferential orientations of organic CH₃NH₃⁺ cations. Among all atomistic interactions, electrostatic interactions dominate thermal conductivities in ionic MAPbI₃ crystals. Furthermore, thermal conductivities of general hybrid perovskites MABX₃ (B = Pb, Sn; X = I, Br) have been qualitatively estimated and found that Sn‐ or Br‐based perovskites possess higher thermal conductivities than Pb‐ or I‐based ones due to their much higher elastic stiffness. This study inspires optimal selections and rational designs of ionic components for hybrid perovskites with desired thermal conductivity for thermally‐stable photovoltaic or highly‐efficient thermoelectric energy harvesting/conversion applications.     

Phonon Scattering and Thermal Conductivity in p‐Type Nanostructured PbTe‐BaTe Bulk Thermoelectric Materials

Transmission electron microscopy studies show that a PbTe‐BaTe bulk thermoelectric system represents the coexistence of solid solution and nanoscale BaTe precipitates. The observed significant reduction in the thermal conductivity is attributed to the enhanced phonon scattering by the combination of substitutional point defects in the solid solution and the presence of high spatial density of nanoscale precipitates. In order to differentiate the role of nanoscale precipitates and point defects in reducing lattice thermal conductivity, a modified Callaway model is proposed, which highlights the contribution of point defect scattering due to solid solution in addition to that of other relevant microstructural constituents. Calculations indicate that in addition to a 60% reduction in lattice thermal conductivity by nanostructures, point defects are responsible for about 20% more reduction and the remaining reduction is contributed by the collective of dislocation and strain scattering. These results underscore the need for tailoring integrated length‐scales for enhanced heat‐carrying phonon scattering in high performance thermoelectrics.     

Thermoelectric Properties of Half-Heusler Bismuthides ZrCo<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ni<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Bi (<Emphasis Type="Italic">x</Emphasis> = 0.0 to 0.1)

The usefulness of half-Heusler (HH) alloys as thermoelectrics has been mainly limited by their relatively large thermal conductivity, which is a key issue despite their high thermoelectric power factors. In this regard, Bi-containing half-Heusler alloys are particularly appealing, because they are, potentially, of low thermal conductivity. One such a material is ZrCoBi. We prepared pure and Ni-doped ZrCoBi by a solid-state reaction. To evaluate thermoelectric potential we measured electrical resistivity (ρ = 1/σ) and thermopower (σ) up to 1000 K and thermal conductivity (κ) up to 300 K. Our measurements indicate that for these alloys resistivity of approximately a few mΩ cm and thermopower larger than a hundred μV K⁻¹ are possible. Low κ values are also possible. On the basis of these data we conclude that this system has a potential to be optimized further, despite the low power factors (α ² σT) we have currently measured.     

Employing Interfaces with Metavalently Bonded Materials for Phonon Scattering and Control of the Thermal Conductivity in TAGS‐x Thermoelectric Materials

The thermoelectric compound (GeTe)_x(AgSbTe₂)_1?x, in short (TAGS‐x), is investigated with a focus on two stoichiometries, i.e., TAGS‐50 and TAGS‐85. TAGS‐85 is currently one of the most studied thermoelectric materials with great potential for thermoelectric applications. Yet, surprisingly, the lowest thermal conductivity is measured for TAGS‐50, instead of TAGS‐85. To explain this unexpected observation, atom probe tomography (APT) measurements are conducted on both samples, revealing clusters of various compositions and sizes. The most important role is attributed to Ag₂Te nanoprecipitates (NPs) found in TAGS‐50. In contrast to the Ag₂Te NPs, the matrix reveals an unconventional bond breaking mechanism. More specifically, a high probability of multiple events (PME) of ≈60% is observed for the matrix by APT. Surprisingly, the PME value decreases abruptly to ≈20–30% for the Ag₂Te NPs. These differences can be attributed to differences in chemical bonding. The precipitates' PME value is indicative of normal bonding, i.e., covalent bonding with normal optical modes, while materials with this unconventional bond breaking found in the matrix are characterized by metavalent bonding. This implies that the interface between the metavalently bonded matrix and covalently bonded Ag₂Te NP is partly responsible for the reduced thermal conductivity in TAGS‐50.     

Doping Dependent In‐Plane and Cross‐Plane Thermoelectric Performance of Thin n‐Type Polymer P(NDI2OD‐T2) Films

Thermoelectric generators pose a promising approach in renewable energies as they can convert waste heat into electricity. In order to build high efficiency devices, suitable thermoelectric materials, both n‐ and p‐type, are needed. Here, the n‐type high‐mobility polymer poly[N,N′‐bis(2‐octyldodecyl)naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene) (P(NDI2OD‐T2)) is focused upon. Via solution doping with 4‐(1,3‐dimethyl‐2,3‐dihydro‐1H‐benzoimidazol‐2‐yl)‐N,N‐diphenylaniline (N‐DPBI), a maximum power factor of (1.84 ± 0.13) µW K^?2 m^?1 is achieved in an in‐plane geometry for 5 wt% dopant concentration. Additionally, UV–vis spectroscopy and grazing‐incidence wide‐angle X‐ray scattering are applied to elucidate the mechanisms of the doping process and to explain the discrepancy in thermoelectric performance depending on the charge carriers being either transported in‐plane or cross‐plane. Morphological changes are found such that the crystallites, built‐up by extended polymer chains interacting via lamellar and π–π stacking, re‐arrange from face‐ to edge‐on orientation upon doping. At high doping concentrations, dopant molecules disturb the crystallinity of the polymer, hindering charge transport and leading to a decreased power factor at high dopant concentrations. These observations explain why an intermediate doping concentration of N‐DPBI leads to an optimized thermoelectric performance of P(NDI2OD‐T2) in an in‐plane geometry as compared to the cross‐plane case.     

Unveiling the Correlation between the Crystalline Structure of M‐Filled CoSb3 (M = Y,K, Sr) Skutterudites and Their Thermoelectric Transport Properties

Skutterudite‐type pnictides based on CoSb₃ are promising semiconductor materials for thermoelectric applications. An exhaustive structural characterization by synchrotron X‐ray powder diffraction of different M‐filled CoSb₃ (M = Y, K, Sr, La, Ce, Yb) skutterudites, with a panoply of M atoms with very different chemical nature, allows to better understand the effects of filling from a crystallo‐chemical point of view. These analyses focus on the correlation of chemical and structural features with the enhanced thermoelectric properties displayed by certain families of filled‐CoSb₃ skutterudites. These are mainly determined by Sb positional parameters, yielding Oftedal plots that depend on the filling fraction, ionic state, and atomic radius of the filler. Together with the distortion of [Sb₄] rings and [CoSb₆] octahedra present in the skutterudite structure, these results are linked to the band‐convergence concept and its influence on the thermoelectric transport properties. Here, the structural changes observed in the different chemical compositions are relevant to understand the improved thermoelectric performance of single partially filled n‐type skutterudites.     

Thermoelectric Properties of Chevrel-Phase Sulfides M<Subscript><Emphasis Type=Italic>x</Emphasis></Subscript>Mo<Subscript>6</Subscript>S<Subscript>8</Subscript> (M: Cr,Mn, Fe,Ni)

Chevrel-phase sulfides M _x Mo₆S₈ (M, Cr, Mn, Fe, Ni; x: 1.3, 2.0) were prepared by reacting appropriate amounts of M, Mo, and MoS₂ powders. The samples were then consolidated by pressure-assisted sintering to fabricate dense compacts. While Cr_1.3Mo₆S₈ crystallized in a triclinic structure, Mn_1.3Mo₆S₈, Fe_1.3Mo₆S₈, and Ni_2.0Mo₆S₈ crystallized in a hexagonal structure. The Seebeck coefficient, electrical resistivity, and thermal conductivity of the sintered samples were measured over the temperature range of 300 K to 973 K. All the samples exhibited a positive Seebeck coefficient. The Seebeck coefficient, electrical resistivity, and thermal conductivity of M_1.3Mo₆S₈ (M: Cr, Mn, Fe) were almost identical and increased with temperature. However, the corresponding values and temperature dependent behavior of Ni_2.0Mo₆S₈ were different from those of M_1.3Mo₆S₈ (M: Cr, Mn, Fe). For Ni_2.0Mo₆S₈, as temperature increased, the Seebeck coefficient and thermal conductivity increased while the electrical resistivity decreased. The highest value of the thermoelectric figure of merit (0.17) was observed in Cr_1.3Mo₆S₈ at 973 K.     

Thermoelectric Characterization of (Ga,In)<Subscript>2</Subscript>Te<Subscript>3</Subscript> with Self-Assembled Two-Dimensional Vacancy Planes

The key properties for the design of high-efficiency thermoelectric materials are a low thermal conductivity and a large Seebeck coefficient with moderate electrical conductivity. Recent developments in nanotechnology and nanoscience are leading to breakthroughs in the field of thermoelectrics. The goal is to create a situation where phonon pathways are disrupted due to nanostructures in “bulk” materials. Here we introduce promising materials: (Ga,In)₂Te₃ with unexpectedly low thermal conductivity, in which certain kinds of superlattice structures naturally form. Two-dimensional vacancy planes with approximately 3.5-nm intervals exist in Ga₂Te₃, scattering phonons efficiently and leading to a very low thermal conductivity.     

Nanocasting of Mesoporous In‐TM (TM = Co,Fe, Mn) Oxides: Towards 3D Diluted‐Oxide Magnetic Semiconductor Architectures

Transition metal (Co, Fe, Mn)‐doped In₂O_3?y mesoporous oxides are synthesized by nanocasting using mesoporous silica as hard templates. 3D ordered mesoporous replicas are obtained after silica removal in the case of the In‐Co and In‐Fe oxide powders. During the conversion of metal nitrates into the target mixed oxides, Co, Fe, and Mn ions enter the lattice of the In₂O₃ bixbyite phase via isovalent or heterovalent cation substitution, leading to a reduction in the cell parameter. In turn, non‐negligible amounts of oxygen vacancies are also present, as evidenced from Rietveld refinements of the X‐ray diffraction patterns. In addition to (In_1?xTM_x)₂O_3?y, minor amounts of Co₃O₄, α‐Fe₂O₃, and Mn_xO_y phases are also detected, which originate from the remaining TM cations not forming part of the bixbyite lattice. The resulting TM‐doped In₂O_3?y mesoporous materials show a ferromagnetic response at room temperature, superimposed on a paramagnetic background. Conversely, undoped In₂O_3?y exhibits a mixed diamagnetic‐ferromagnetic behavior with much smaller magnetization. The influence of the oxygen vacancies and the doping elements on the magnetic properties of these materials is discussed. Due to their 3D mesostructural geometrical arrangement and their room‐temperature ferromagnetic behavior, mesoporous oxide‐diluted magnetic semiconductors may become smart materials for the implementation of advanced components in spintronic nanodevices.     

Cu7S4/MxSy (M=Cd,Ni, and Mn) Janus Atomic Junctions for Plasmonic Energy Upconversion Boosted Multi-Functional Photocatalysis

Rational design/synthesis of atomic-level-engineered Janus junctions for sunlight-impelled high-performance photocatalytic generation of clean fuels (e.g., H₂O₂ and H₂) and valuable chemicals are of great significance. Especially, it is appealing but challenging to acquire accurately-engineered Janus atomic junctions (JAJs) for simultaneously realizing the plasmonic energy upconversion with near-infrared (NIR) light and direct Z-scheme charge transfer with visible light. Here, a range of new Cu₇S₄/M_xS_y (M=Cd, Ni, and Mn) JAJs are designed/synthesized via a cation-exchange route using Cu₇S₄ hexagonal nanodisks as templates. All Cu₇S₄/M_xS_y JAJs show apparently-enhanced photocatalytic H₂O₂ evolution compared to Cu₇S₄ in pure water. Notably, optimized Cu₇S₄/CdS (CCS) JAJ exhibits the outstanding H₂O₂ evolution rate (2.93 mmol g⁻¹ h⁻¹) in benzyl alcohol aqueous solution, due to the following factors: i) NIR light-impelled plasmonic energy upconversion induced H₂O₂ evolution, revealed by ultrafast transient absorption spectroscopy; ii) visible-light-driven direct Z-scheme charge migration, confirmed by in situ X-ray photoelectron spectroscopy. Besides, three different reaction pathways for H₂O₂ evolution are disclosed by in situ electron spin resonance spectroscopy and quenching experiments. Finally, CCS JAJ also exhibits super-high rates on H₂ and benzaldehyde co-generation using visible-NIR light or NIR light. This work highlights the significance of atomic-scale interface engineering for solar-to-chemical conversion.     

General Formation of MS (M = Ni,Cu, Mn) Box‐in‐Box Hollow Structures with Enhanced Pseudocapacitive Properties

Complex hollow structures of metal sulfides could be promising materials for energy storage devices such as supercapacitors and lithium‐ion batteries. However, it is still a great challenge to fabricate well‐defined metal sulfides hollow structures with multi‐shells, hierarchical architectures, and non‐spherical shape. In this work, a template‐engaged strategy is developed to synthesize hierarchical NiS box‐in‐box hollow structures with double‐shells. The NiS box‐in‐box hollow structures constructed by ultrathin nanosheets are evaluated as electrode materials for supercapacitors. As expected, the NiS box‐in‐box hollow structures exhibit excellent rate performance and impressive cycling stability due to their unique nano‐architecture. More importantly, the synthetic method can be easily extended to synthesize other transition metal sulfides box‐in‐box hollow structures. For example, we have also successfully synthesized similar CuS and MnS box‐in‐box hollow structures. The present work makes a significant contribution to the design and synthesis of transition metal sulfides hollow structures with non‐spherical shape and complex architecture, as well as their potential applications in electrochemical energy storage.     

Size‐Controlled Synthesis of Cu2‐xE (E = S,Se) Nanocrystals with Strong Tunable Near‐Infrared Localized Surface Plasmon Resonance and High Conductivity in Thin Films

A facile method for preparing highly self‐doped Cu_2‐xE (E = S, Se) nanocrystals (NCs) with controlled size in the range of 2.8–13.5 nm and 7.2–16.5 nm, for Cu_2‐xS and Cu_2‐xSe, respectively, is demonstrated. Strong near‐infrared localized surface plasmon resonance absorption is observed in the NCs, indicating that the as‐prepared particles are heavily p‐doped. The NIR plasmonic absorption is tuned by varying the amount of oleic acid used in synthesis. This effect is attributed to a reduction in the number of free carriers through surface interaction of the deprotonated carboxyl functional group of oleic acid with the NCs. This approach provides a new pathway to control both the size and the cationic deficiency of Cu_2‐xSe and Cu_2‐xS NCs. The high electrical conductivity exhibited by these NPs in metal‐semiconductor‐metal thin film devices shows promise for applications in printable field‐effect transistors and microelectronic devices.