Strongly Anisotropic Thermal Conductivity of Free‐Standing Reduced Graphene Oxide Films Annealed at High Temperature

Thermal conductivity of free‐standing reduced graphene oxide films subjected to a high‐temperature treatment of up to 1000 °C is investigated. It is found that the high‐temperature annealing dramatically increases the in‐plane thermal conductivity, K, of the films from ≈3 to ≈61 W m^?1 K^?1 at room temperature. The cross‐plane thermal conductivity, K_⊥, reveals an interesting opposite trend of decreasing to a very small value of ≈0.09 W m^?1 K^?1 in the reduced graphene oxide films annealed at 1000 °C. The obtained films demonstrate an exceptionally strong anisotropy of the thermal conductivity, K/K_⊥ ≈ 675, which is substantially larger even than in the high‐quality graphite. The electrical resistivity of the annealed films reduces to 1–19 Ω □^?1. The observed modifications of the in‐plane and cross‐plane thermal conductivity components resulting in an unusual K/K_⊥ anisotropy are explained theoretically. The theoretical analysis suggests that K can reach as high as ≈500 W m^?1 K^?1 with the increase in the sp² domain size and further reduction of the oxygen content. The strongly anisotropic heat conduction properties of these films can be useful for applications in thermal management.     

Understanding of the Extremely Low Thermal Conductivity in High‐Performance Polycrystalline SnSe through Potassium Doping

P‐type polycrystalline SnSe and K_0.01Sn_0.99Se are prepared by combining mechanical alloying (MA) and spark plasma sintering (SPS). The highest ZT of ≈0.65 is obtained at 773 K for undoped SnSe by optimizing the MA time. To enhance the electrical transport properties of SnSe, K is selected as an effective dopant. It is found that the maximal power factor can be enhanced significantly from ≈280 μW m^?1 K^?2 for undoped SnSe to ≈350 μW m^?1 K^?2 for K‐doped SnSe. It is also observed that the thermal conductivity of polycrystalline SnSe can be enhanced if the SnSe powders are slightly oxidized. Surprisingly, after K doping, the absence of Sn oxides at grain boundaries and the presence of coherent nanoprecipitates in the SnSe matrix contribute to an impressively low lattice thermal conductivity of ≈0.20 W m^?1 K^?1 at 773 K along the sample section perpendicular to pressing direction of SPS. This extremely low lattice thermal conductivity coupled with the enhanced power factor results in a record high ZT of ≈1.1 at 773 K along this direction in polycrystalline SnSe.     

Analysis of Ce‐ and Yb‐Doped TAGS‐85 Materials with Enhanced Thermoelectric Figure of Merit

Doping of TAGS‐85 with 1 at% Ce or Yb forms a dilute magnetic semiconductor system with non‐interacting localized magnetic moments that obey the Curie law. X‐ray diffraction patterns and slight broadening in ¹²⁵Te NMR, attributed to paramagnetic effects, suggest that Ce and Yb atoms are incorporated into the lattice. ¹²⁵Te NMR spin‐lattice relaxation and Hall effect show similar hole concentrations of ≈10²¹ cm^?3. At 700 K, the electric conductivity of the Ce‐ and Yb‐doped samples is similar to that of neat TAGS‐85, while the thermal conductivity and the Seebeck coefficient are larger by 6% and 16%, respectively. Possible mechanisms responsible for the observed increase in thermopower may include i) formation of resonance states near the Fermi level and ii) carrier scattering by lattice distortions and/or by paramagnetic ions. Due to the increase in the Seebeck coefficient up to 205 μV K^?1, the thermoelectric power factor of Ce‐ and Yb‐doped samples reaches 36 μW cm^?1 K^?2, which is larger than that measured for neat TAGS‐85, 27 μW cm^?1 K^?2. The increase in the Seebeck coefficient overcomes the increase in the thermal conductivity, resulting in a total increase of the figure of merit by ≈25% at 700 K compared to that observed for neat TAGS‐85.     

Thermal Properties of the Binary‐Filler Hybrid Composites with Graphene and Copper Nanoparticles

The thermal properties of epoxy‐based binary composites comprised of graphene and copper nanoparticles are reported. It is found that the “synergistic” filler effect, revealed as a strong enhancement of the thermal conductivity of composites with the size‐dissimilar fillers, has a well‐defined filler loading threshold. The thermal conductivity of composites with a moderate graphene concentration of f_g = 15 wt% exhibits an abrupt increase as the loading of copper nanoparticles approaches f_Cu ≈ 40 wt%, followed by saturation. The effect is attributed to intercalation of spherical copper nanoparticles between the large graphene flakes, resulting in formation of the highly thermally conductive percolation network. In contrast, in composites with a high graphene concentration, f_g = 40 wt%, the thermal conductivity increases linearly with addition of copper nanoparticles. A thermal conductivity of 13.5 ± 1.6 Wm^?1K^?1 is achieved in composites with binary fillers of f_g = 40 wt% and f_Cu = 35 wt%. It has also been demonstrated that the thermal percolation can occur prior to electrical percolation even in composites with electrically conductive fillers. The obtained results shed light on the interaction between graphene fillers and copper nanoparticles in the composites and demonstrate potential of such hybrid epoxy composites for practical applications in thermal interface materials and adhesives.     

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.     

High Thermoelectric Performance of ZnO by Coherent Phonon Scattering and Optimized Charge Transport

ZnO is identified as a potentially attractive n-type oxide thermoelectric material due to its abundance, nontoxicity, and a high degree of stability. However, working with ZnO is challenging due to its high thermal conductivity from its strong ionic bonds and low electrical conductivity due to its low charge concentrations. Here, it is demonstrated that the electrical and thermal transport properties of ZnO can be simultaneously improved via the successful doping of Al and ZnS coating. The ZnS coating in Al-doped ZnO is observed and analyzed through microstructure and spectroscopic studies. The power factor for 1% ZnS-coated Zn_0.98Al_0.02O is increased to ≈0.75 mW m⁻¹ K⁻² at 1073 K, 161% higher than pure ZnO. This enhancement in the power factor can be explained by the aliovalent Al³⁺ doping and modifications in intrinsic defects, leading to an increased carrier concentration. Interestingly, ZnS coating significantly reduces lattice thermal conductivity to ≈2.31 W m⁻¹ K⁻¹ at 1073 K for 2% ZnS-coated Zn_0.98Al_0.02O, a 62% decrease over pure ZnO. This large reduction in lattice thermal conductivity can be elucidated based on coherent phonon scattering via Callaway's model. Overall, the figure of merit, zT, increases to 0.2 in 2% ZnS-coated Zn_0.98Al_0.02O, which is 272% higher than pure ZnO at 1073 K.     

Coreless Fiber‐Based Whispering‐Gallery‐Mode Assisted Lasing from Colloidal Quantum Well Solids

Whispering gallery mode (WGM) resonators are shown to hold great promise to achieve high‐performance lasing using colloidal semiconductor nanocrystals (NCs) in solution phase. However, the low packing density of such colloidal gain media in the solution phase results in increased lasing thresholds and poor lasing stability in these WGM lasers. To address these issues, here optical gain in colloidal quantum wells (CQWs) is proposed and shown in the form of high‐density close‐packed solid films constructed around a coreless fiber incorporating the resulting whispering gallery modes to induce gain and waveguiding modes of the fiber to funnel and collect light. In this work, a practical method is presented to produce the first CQW‐WGM laser using an optical fiber as the WGM cavity platform operating at low thresholds of ≈188 µJ cm^?2 and ≈1.39 mJ cm^?2 under one‐ and two‐photon absorption pumped, respectively, accompanied with a record low waveguide loss coefficient of ≈7 cm^?1 and a high net modal gain coefficient of ≈485 cm^?1. The spectral characteristics of the proposed CQW‐WGM resonator are supported with a numerical model of full electromagnetic solution. This unique CQW‐WGM cavity architecture offers new opportunities to achieve simple high‐performance optical resonators for colloidal lasers.     

A Promising Radiation Thermal Protection Coating Based on Lamellar Porous Ca-Cr co-Doped Y3NbO7 Ceramic

Dissipation of heat efficiently from a hot object via radiation while minimizing the inward heat conduction is the key requirement of radiation thermal protection. In this study, a Ca-Cr co-doped Y₃NbO₇ coating with lamellar porous structure is fabricated, which shows an ultra-low thermal conductivity (<0.7 W m⁻¹ K⁻¹) and near-unity emissivity (>0.9) across a broad wavelength range of ≈1–24 µm. This record high emissivity to thermal conductivity ratio (≈1.3) is experimentally and theoretically revealed from a multi-scale perspective. The diffusoin-mediated thermal conduction feature of niobates combined with lamellar porous structure of the coating reduces its thermal conductivity to an impressive 0.5 W m⁻¹ K⁻¹ at 25 °C, surpassing the theoretical amorphous limitation of 0.72 W m⁻¹ K⁻¹. Experiments and FDTD calculation results demonstrate that the intrinsic emissivity dips at shallow extinction wavelengths (1 and 8 µm) and strong phonon-polariton resonances wavelengths (>13 µm) can be effectively compensated by the multiple scattering/absorption and gradual modulation of conical shape/effective refractive index induced by surface micro-protrusion structures, respectively. Furthermore, the coating exhibits robust mechanical and thermal stability with a high bonding strength (18.3 MPa) and thermal expansion coefficient (≈11 × 10⁻⁶ K⁻¹ at 1200 °C) comparable to YSZ, showing great potential in the radiation thermal protection field.     

Ultrathin Flexible Graphene Film: An Excellent Thermal Conducting Material with Efficient EMI Shielding

As the portable device hardware has been increasing at a noticeable rate, ultrathin thermal conducting materials (TCMs) with the combination of high thermal conductivity and excellent electromagnetic interface (EMI) shielding performance, which are used to efficiently dissipate heat and minimize EMI problems generated from electronic components (such as high speed processors), are urgently needed. In this work, graphene oxide (GO) films are fabricated by direct evaporation of GO suspension under mild heating, and ultrathin graphite‐like graphene films are produced by graphitizing GO films. Further investigation demonstrates that the resulting graphene film with only ≈8.4 μm in thickness not only possesses excellent EMI shielding effectiveness of ≈20 dB and high in‐plane thermal conductivity of ≈1100 W m^‐1 K^‐1, but also shows excellent mechanical flexibility and structure integrity during bending, indicating that the graphitization of GO film could be considered as a new alternative way to produce excellent TCMs with efficient EMI shielding.     

Intrinsically Low Thermal Conductivity in BiSbSe3: A Promising Thermoelectric Material with Multiple Conduction Bands

Bi₂Se₃, as a Te‐free alternative of room‐temperature state‐of‐the‐art thermoelectric (TE) Bi₂Te₃, has attracted little attention due to its poor electrical transport properties and high thermal conductivity. Interestingly, BiSbSe₃, a product of alloying 50% Sb on Bi sites, shows outstanding electron and phonon transports. BiSbSe₃ possesses orthorhombic structure and exhibits multiple conduction bands, which can be activated when the carrier density is increased as high as ≈3.7 × 10²⁰ cm^?3 through heavily Br doping, resulting in simultaneously enhancing the electrical conductivities and Seebeck coefficients. Meanwhile, an extremely low thermal conductivity (≈0.6–0.4 W m^?1 K^?1 at 300–800 K) is found in BiSbSe₃. Both first‐principles calculations and elastic properties measurements show the strong anharmonicity and support the ultra‐low thermal conductivity of BiSbSe₃. Finally, a maximum dimensionless figure of merit ZT ～ 1.4 at 800 K is achieved in BiSb(Se_0.94Br_0.06)₃, which is comparable to the most n‐type Te‐free TE materials. The present results indicate that BiSbSe₃ is a new and a robust candidate for TE power generation in medium‐temperature range.     

Gas Diffusion,Energy Transport,and Thermal Accommodation in Single‐Walled Carbon Nanotube Aerogels

The thermal conductivity of gas‐permeated single‐walled carbon nanotube (SWCNT) aerogel (8 kg m^?3 density, 0.0061 volume fraction) is measured experimentally and modeled using mesoscale and atomistic simulations. Despite the high thermal conductivity of isolated SWCNTs, the thermal conductivity of the evacuated aerogel is 0.025 ± 0.010 W m^?1 K^?1 at a temperature of 300 K. This very low value is a result of the high porosity and the low interface thermal conductance at the tube–tube junctions (estimated as 12 pW K^?1). Thermal conductivity measurements and analysis of the gas‐permeated aerogel (H₂, He, Ne, N₂, and Ar) show that gas molecules transport energy over length scales hundreds of times larger than the diameters of the pores in the aerogel. It is hypothesized that inefficient energy exchange between gas molecules and SWCNTs gives the permeating molecules a memory of their prior collisions. Low gas‐SWCNT accommodation coefficients predicted by molecular dynamics simulations support this hypothesis. Amplified energy transport length scales resulting from low gas accommodation are a general feature of CNT‐based nanoporous 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.     

Simultaneous Enhancement in Electrical Conductivity and Thermopower of n‐Type NiETT/PVDF Composite Films by Annealing

Nickel ethenetetrathiolate (NiETT) polymers are promising n‐type thermoelectric (TE) materials, but their insolubility requires the use of an inert polymer matrix to form films, which is detrimental to the TE performance. In this work, the use of thermal annealing as a post‐treatment process simultaneously enhances the electrical conductivity from 6 ± 2 to 23 ± 3 S cm^?1 and thermopower from ?28 ± 3 to ?74 ± 4 µV K^?1 for NiETT/PVDF composite films. Spectroscopic characterization reveals that the underlying mechanism involves removal of residual solvent and volatile impurities (carbonyl sulfide and water) in the NiETT polymer backbone. Additionally, microscopic characterization reveals morphological changes caused by a densification of the film that improves chain packing. These effects result in a 25 × improvement in power factor from 0.5 to 12.5 µW m^?1 K^?2 for NiETT/PVDF films and provide insight into the composition of these coordination polymers that maintain their stability under ambient conditions.     

Anisotropic Thermal Conductive Composite by the Guided Assembly of Boron Nitride Nanosheets for Flexible and Stretchable Electronics

Owing to the growing demand for highly integrated electronics, anisotropic heat dissipation of thermal management material is a challenging and promising technique. Moreover, to satisfy the needs for advancing flexible and stretchable electronic devices, maintaining high thermal conductivity during the deformation of electronic materials is at issue. Presented here is an effective assembly technique to realize a continuous array of boron nitride (BN) nanosheets on tetrahedral structures, creating 3D thermal paths for anisotropic dissipation integrated with deformable electronics. The tetrahedral structures, with a fancy wavy shaped cross‐section, guarantee flexibility and stretchability, without the degradation of thermal conductivity during the deformation of the composite film. The structured BN layer in the composites induces a high thermal conductivity of 1.15 W m^?1 K^?1 in the through‐plane and 11.05 W m^?1 K^?1 in the in‐plane direction at the low BN fraction of 16 wt%, which represent 145% and 83% increases over the randomly mixing method, respectively. Furthermore, this structured BN composite maintains thermal dissipation property with 50% strain of the original length of composite. Various electronic device demonstrations provide exceptional heat dissipation capabilities, including thin film silicon transistor and light‐emitting diode on flexible and stretchable composite, respectively.     

Bulk Hexagonal Boron Nitride with a Quasi‐Isotropic Thermal Conductivity

Hexagonal boron nitride (BN) is electrically insulating and has a high in‐plane thermal conductivity. However, it has a very low cross‐plane thermal conductivity which limits its application for efficient heat dissipation. Here, large BN pellets with a quasi‐isotropic thermal conductivity are produced from BN nanosheets using a spark plasma sintering (SPS) technique. The BN pellets have the same thermal conductivity from both perpendicular and parallel directions to the pellet surface. The high quasi‐isotropic thermal conductivity of the bulk BN is attributed to a quasi‐isotropic structure formed during the SPS process in which the charged BN nanosheets form large sheets in all directions under two opposite forces of SPS compression and electric field. The pellet sintered at 2300 °C has a very high cross‐section thermal conductivity of 280 W m^?1 K^?1 (parallel to the SPS pressing direction) and exhibits superior heat dissipation performance due to more efficient heat transfer in the vertical direction.     

Thermally Conductive Reduced Graphene Oxide Thin Films for Extreme Temperature Sensors

Reduced graphene oxide (RGO) films are promising in applications ranging from electronics to flexible sensors. Though high electrical and thermal conductivities have been reported for RGO films, existing thermal conductivity data for RGO films show large variations from 30 to 2600 W m^?1 K^?1. Further, there is a lack of data at low temperatures (<300 K), which is critical for the understanding of thermal transport mechanisms. In this work, a temperature‐dependent study of thermal (10–300 K) and electrical (10–3000 K) transport in annealed RGO films indicates the potential application of RGO films for sensing temperatures across an extremely wide range. The room‐temperature thermal conductivity increases significantly from 46.1 to 118.7 W m^?1 K^?1 with increasing annealing temperature from 1000 to 3000 K with a corresponding increase in the electrical conductivity from 5.2 to 1481.0 S cm^?1. In addition, films reduced at 3000 K are promising for sensing extreme temperatures as demonstrated through the measured electrical resistivity from 10 to 3000 K. Sensors based on RGO films are advantageous over conventional temperature sensors due to the wide temperature range and flexibility. Thus, this material is useful in many applications including flexible electronics and thermal management systems.     

Thermal Properties of Lipid Bilayers Determined Using Upconversion Nanothermometry

Luminescent nanomaterials have shown promise for thermal sensing in bio‐applications, yet little is known of the role of organic coatings such as supported lipid bilayers on the thermal conductivity between the nanomaterial and its environment. Additionally, since the supported lipid bilayer mimics the cell membrane, its thermal properties are fundamentally important to understand the spatial variations of temperature and heat transfer across membranes. Herein, a new approach is described that enables direct measurement of these thermal properties using a LiYF₄:Er³⁺/Yb³⁺ upconverting nanoparticle encapsulated within a conformal supported lipid bilayer and dispersed in water as a temperature probe yielding the temperature gradient across the bilayer. The thermal conductivity of the lipid bilayer is measured as a function of the temperature, being 0.20 ± 0.02 W m^?1 K^?1 at 300 K. For the uncapped nanoparticles dispersed in water, the temperature dependence of the thermal conductivity is also measured in the 300–314 K range as [0.63–0.69] ± 0.11 W m^?1 K^?1. Using a lumped elements model, the directional heat transfer is calculated at each of the system interfaces, namely, nanoparticle–bilayer and bilayer–nanofluid, opening a new avenue to understand the membrane biophysical properties as well as the thermal properties of organic and polymer coatings.     

Glass‐Like Through‐Plane Thermal Conductivity Induced by Oxygen Vacancies in Nanoscale Epitaxial La0.5Sr0.5CoO3−δ

Ultrafast time‐domain thermoreflectance (TDTR) is utilized to extract the through‐plane thermal conductivity (Λ _LSCO) of epitaxial La_0.5Sr_0.5CoO_3?δ (LSCO) of varying thickness (<20 nm) on LaAlO₃ and SrTiO₃ substrates. These LSCO films possess ordered oxygen vacancies as the primary means of lattice mismatch accommodation with the substrate, which induces compressive/tensile strain and thus controls the orientation of the oxygen vacancy ordering (OVO). TDTR results demonstrate that the room‐temperature Λ _LSCO of LSCO on both substrates (1.7 W m^?1 K^?1) are nearly a factor of four lower than that of bulk single‐crystal LSCO (6.2 W m^?1 K^?1). Remarkably, this approaches the lower limit of amorphous oxides (e.g., 1.3 W m^?1 K^?1 for glass), with no dependence on the OVO orientation. Through theoretical simulations, origins of the glass‐like thermal conductivity of LSCO are revealed as a combined effect resulting from oxygen vacancies (the dominant factor), Sr substitution, size effects, and the weak electron/phonon coupling within the LSCO film. The absence of OVO dependence in the measured Λ _LSCO is rationalized by two main effects: (1) the nearly isotropic phononic thermal conductivity resulting from the imperfect OVO planes when δ is small; (2) the missing electronic contribution to Λ _LSCO along the through‐plane direction for these ultrathin LSCO films on insulating substrates.     

Room‐Temperature Metallic Fusion‐Induced Layer‐by‐Layer Assembly for Highly Flexible Electrode Applications

To fabricate flexible electrodes, conventional silver (Ag) nanomaterials have been deposited onto flexible substrates, but the formed electrodes display limited electrical conductivity due to residual bulky organic ligands, and thus postsintering processes are required to improve the electrical conductivity. Herein, an entirely different approach is introduced to produce highly flexible electrodes with bulk metal–like electrical conductivity: the room‐temperature metallic fusion of multilayered silver nanoparticles (NPs). Synthesized tetraoctylammonium thiosulfate (TOAS)‐stabilized Ag NPs are deposited onto flexible substrates by layer‐by‐layer assembly involving a perfect ligand‐exchange reaction between bulky TOAS ligands and small tris(2‐aminoethyl)amine linkers. The introduced small linkers substantially reduce the separation distance between neighboring Ag NPs. This shortened interparticle distance, combined with the low cohesive energy of Ag NPs, strongly induces metallic fusion between the close‐packed Ag NPs at room temperature without additional treatments, resulting in a high electrical conductivity of ≈1.60 × 10⁵ S cm^?1 (bulk Ag: ≈6.30 × 10⁵ S cm^?1). Furthermore, depositing the TOAS–Ag NPs onto cellulose papers through this approach can convert the insulating substrates into highly flexible and conductive papers that can be used as 3D current collectors for energy‐storage devices.     

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.