The Criteria for Beneficial Disorder in Thermoelectric Solid Solutions

Forming solid solutions has long been considered an effective approach for good thermoelectrics because the lattice thermal conductivities are lower than those of the constituent compounds due to phonon scattering from disordered atoms. However, this effect could also be compensated by a reduction in carrier mobility due to electron scattering from the same disorder. Using a detailed study of n‐type (PbTe)_1–x (PbSe)_x solid solution (0 ≤ x ≤ 1) as a function of composition, temperature, and doping level, quantitative modeling of transport properties reveals the important parameters characterizing these effects. Based on this analysis, a general criterion for the improvement of zT due to atomic disorder in solid solutions is derived and can be applied to several thermoelectric solid solutions, allowing a convenient prediction of whether better thermoelectric performance could be achieved in a given solid solution. Alloying is shown to be most effective at low temperatures and in materials that are unfavorable for thermoelectrics in their unalloyed forms: high lattice thermal conductivity (stiff materials with low Grüneisen parameters) and high deformation potential.     

Microstructure‐Lattice Thermal Conductivity Correlation in Nanostructured PbTe0.7S0.3 Thermoelectric Materials

The reduction of thermal conductivity, and a comprehensive understanding of the microstructural constituents that cause this reduction, represent some of the important challenges for the further development of thermoelectric materials with improved figure of merit. Model PbTe‐based thermoelectric materials that exhibit very low lattice thermal conductivity have been chosen for this microstructure–thermal conductivity correlation study. The nominal PbTe_0.7S_0.3 composition spinodally decomposes into two phases: PbTe and PbS. Orderly misfit dislocations, incomplete relaxed strain, and structure‐modulated contrast rather than composition‐modulated contrast are observed at the boundaries between the two phases. Furthermore, the samples also contain regularly shaped nanometer‐scale precipitates. The theoretical calculations of the lattice thermal conductivity of the PbTe_0.7S_0.3 material, based on transmission electron microscopy observations, closely aligns with experimental measurements of the thermal conductivity of a very low value, ～0.8 W m^?1 K^?1 at room temperature, approximately 35% and 30% of the value of the lattice thermal conductivity of either PbTe and PbS, respectively. It is shown that phase boundaries, interfacial dislocations, and nanometer‐scale precipitates play an important role in enhancing phonon scattering and, therefore, in reducing the lattice thermal conductivity.     

Effect of Composition on Thermoelectric Properties in PbTe-Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> Composites

The solidification of alloys in the Bi₂Te₃-PbTe pseudobinary system at off- and near-eutectic compositions was investigated for their microstructure and thermoelectric properties. Dendritic and lamellar structures were clearly observed due to the phase separation and the existence of a metastable ternary phase. In this system, three phases with different compositions were observed: binary Bi₂Te₃, PbTe, and metastable PbBi₂Te₄. The Seebeck coefficient, electrical resistivity, and thermal conductivity of ternary alloys as well as binary compounds were measured. The phonon thermal conductivities of Pb-Bi-Te alloys were lower than those in binary PbTe and Bi₂Te₃, which could have resulted from the increased interfacial area between phases due to the existence of the metastable ternary phase and the resultant phase separation.     

Strong Band Bowing Effects and Distinctive Optoelectronic Properties of 2H and 1T′ Phase‐Tunable MoxRe1–xS2 Alloys

Structure and energy band engineering of 2D materials via selective doping or phase modulation provide a significant opportunity to design them for optoelectronic devices. Here, the synthesis of high‐quality Mo_xRe_1–xS₂ alloys with tunable composition and phase structure via chemical vapor deposition growth is reported, and their novel energy band structures and optoelectronic properties are explored. The phase separation and structure reconstruction, which are found to be two serious problems in the synthesis of these alloys, are successfully suppressed through tuning their growth thermodynamics. As a result, the obtained Mo_xRe_1–xS₂ alloys have uniform composition, phase structure, and crystal orientation. Together with X‐ray photoelectron spectroscopy analysis and first‐principle calculation, the Re/Mo doping‐induced Fermi level up‐shift/down‐shift, new electronic states, and “sub‐gap” formation in Mo_xRe_1–xS₂ alloys are revealed. Especially, a strong band bowing effect is discovered in the Mo_xRe_1–xS₂ alloys with structure transition between 1T′ and 2H phases. Furthermore, these alloys reveal tunable conduction behavior from n‐type to bipolar and p‐type in 1T′ phase, as well as novel “bipolar‐like” electron conduction behavior in 2H alloys. The results highlight the unique alloying effects, which do not exist in the single‐phase 2D alloys, and provide the feasibility for potential applications in building novel electronic and optoelectronic devices.     

Bulk Nanostructured Thermoelectric Materials: Preparation,Structure and Properties

Bulk nanostructured materials have recently emerged as a new paradigm for improving the performance of existing thermoelectric materials. Here, we fabricated two kinds of bulk nanostructured thermoelectric materials by a bottom-up strategy and an in situ precipitation method, respectively. Binary PbTe was fabricated by a combination of chemical synthesis and hot pressing. The grain sizes of the hot pressed bulk samples varied from 200 nm to 400 nm, which significantly contributed to the reduction of thermal conductivity due to the enhanced boundary phonon scattering. The highest figure of merit ZT of the binary PbTe sample reached 0.8 at 580 K. Mg₂(Si,Sn) solid solutions have shown great promise for thermoelectric application, due to good thermoelectric properties, non-toxicity, and abundantly available constituent elements. The nanoscale microstructure observation of the compounds showed the existence of nanophases formed in situ, which is believed to be related to the relatively low lattice thermal conductivity in this material system. The highest ZT of Sb-doped Mg₂(Si,Sn) samples reached 1.1 at 770 K.     

Thermal Conductivity and Phonon Scattering Processes of ALD Grown PbTe–PbSe Thermoelectric Thin Films

This work studies the thermal conductivity and phonon scattering processes in a series of n‐type lead telluride‐lead selenide (PbTe–PbSe) nanostructured thin films grown by atomic layer deposition (ALD). The ALD growth of the PbTe–PbSe samples in this work results in nonepitaxial films grown directly on native oxide/Si substrates, where the Volmer–Weber mode of growth promotes grains with a preferred columnar orientation. The ALD growth of these lead‐rich PbTe, PbSe, and PbTe–PbSe thin films results in secondary oxide phases, along with an increase microstructural quality with increased film thickness. The compositional variation and resulting point and planar defects in the PbTe–PbSe nanostructures give rise to additional phonon scattering events that reduce the thermal conductivity below that of the corresponding ALD‐grown control PbTe and PbSe films. Temperature‐dependent thermal conductivity measurements show that the phonon scattering in these ALD‐grown PbTe–PbSe nanostructured materials, along with ALD‐grown PbTe and PbSe thin films, are driven by extrinsic defect scattering processes as opposed to phonon–phonon scattering processes intrinsic to the PbTe or PbSe phonon spectra. The implication of this work is that polycrystalline, nanostructured ALD composites of thermoelectric PbTe–PbSe films are effective in reducing the phonon thermal conductivity, and represent a pathway for further improvement of the figure of merit (ZT), enhancing their thermoelectric application potential.     

Direct Evidence of Cation Disorder in Thermoelectric Lead Chalcogenides PbTe and PbS

The extraordinary thermoelectric properties of lead chalcogenides have attracted huge interest in part due to their unexpected low thermal conductivity. Here, it is shown that anharmonicity and large cation disorder are present in both PbTe and PbS, based on elaborate charge density visualization using synchrotron powder X‐ray diffraction (SPXRD) data analyzed with the maximum entropy method (MEM). In both systems, the cation disorder increases with increasing temperature, whereas the Te/S anions appear to be centered on the expected lattice positions. Even at the lowest temperatures of 105 K, the lead ion is on average displaced by ≈0.2 Å from the rock‐salt lattice position, creating a strong phonon scattering mechanism. These findings provide a clue to understanding the excellent thermoelectric performance of crystals with atomic disorder. The SPXRD–MEM approach can be applied in general opening up for widespread characterization of subtle structural features in crystals with unusual properties.     

High Thermoelectric Performance in PbTe Due to Large Nanoscale Ag2Te Precipitates and La Doping

Thermoelectrics are being rapidly developed for waste heat recovery applications, particularly in automobiles, to reduce carbon emissions. PbTe‐based materials with small (<20 nm) nanoscale features have been previously shown to have high thermoelectric figure‐of‐merit, zT, largely arising from low lattice thermal conductivity particularly at low temperatures. Separating the various phonon scattering mechanisms and the electronic contribution to the thermal conductivity is a serious challenge to understanding, and further optimizing, these nanocomposites. Here we show that relatively large nanometer‐scale (50–200 nm) Ag₂Te precipitates in PbTe can be controlled according to the equilibrium phase diagram and these materials show intrinsic semiconductor behavior with high electrical resistivity, enabling direct measurement of the phonon thermal conductivity. This study provides direct evidence that even large nanometer‐scale microstructures reduce thermal conductivity below that of a macro‐scale composite of saturated alloys with Kapitza‐type interfacial thermal resistance at the same overall composition. Carrier concentration control is achieved with lanthanum doping, enabling independent control of the electronic properties and microstructure. These materials exhibit lattice thermal conductivity which approaches the theoretical minimum above ～650 K, even lower than that found with small nanoparticles. Optimally La‐doped n‐type PbTe‐Ag₂Te nanocomposites exhibit zT > 1.5 at 775 K.     

(Pb1–xCdx)S Nanoparticles Embedded in a Conjugated Organic Matrix,as Studied by Photoluminescence and Light‐Induced X‐ray Photoelectron Spectroscopy

Elliptically shaped (Pb_1–xCd_x)S nanoparticles (NPs) of average size 2.3 × 2.9 nm (minor axis × major axis) have been prepared via reaction of a solid [oligo(p‐phenylene‐ethynylene) dicarboxylate]Pb_0.9Cd_0.1 salt matrix, with gaseous H₂S. A significantly long emission lifetime, with multi‐exponential behavior, is detected in time‐resolved photoluminescence measurements, substantially different from the decay patterns of pure PbS and CdS NPs within the same organic matrix. Evidence for the co‐existence of Cd and Pb within the same particle is provided by light‐induced X‐ray photoelectron spectroscopy.     

Stoichiometry Controlled,Single‐Crystalline Bi2Te3 Nanowires for Transport in the Basal Plane

Thermoelectric Bi₂Te₃ based bulk materials are widely used for solid‐state refrigeration and power‐generation at room temperature. For low‐dimensional and nanostructured thermoelectric materials an increase of the thermoelectric figure of merit ZT is predicted due to quantum confinement and phonon scattering at interfaces. Therefore, the fabrication of Bi₂Te₃ nanowires, thin films, and nanostructured bulk materials has become an important and active field of research. Stoichiometric Bi₂Te₃ nanowires with diameters of 50–80 nm and a length of 56 μm are grown by a potential‐pulsed electrochemical deposition in a nanostructured Al₂O₃ matrix. By transmission electron microscopy (TEM), dark‐field images together with electron diffraction reveal single‐crystalline wires, no grain boundaries can be detected. The stoichiometry control of the wires by high‐accuracy, quantitative enegy‐dispersive X‐ray spectroscopy (EDX) in the TEM instrument is of paramount importance for successfully implementing the growth technology. Combined electron diffraction and EDX spectroscopy in the TEM unambiguously prove the correct crystal structure and stoichiometry of the Bi₂Te₃ nanowires. X‐ray and electron diffraction reveal growth along the [110] and [210] directions and the c axis of the Bi₂Te₃ structure lies perpendicular to the wire axis. For the first time single crystalline, stoichiometric Bi₂Te₃ nanowires are grown that allow transport in the basal plane without being affected by grain boundaries.     

Synthesis of Ceria–Zirconia Nanocrystals with Improved Microstructural Homogeneity and Oxygen Storage Capacity by Hydrolytic Sol–Gel Process in Coordinating Environment

Ceria–zirconia solid solution nanocrystals, (1‐x)CeO₂–xZrO₂, 0 ≤ x ≤ 1, are prepared by sol–gel processing in dodecylamine of solutions obtained by forced hydrolysis of inorganic salts. The as‐prepared nanoparticles have a ceria cubic structure, up to x = 0.35, or are amorphous. Heat‐treatment is carried out at temperatures ranging from 500 to 800 °C, the latter temperature begin suitable to obtain solid solutions throughout the composition range. For all the heating temperatures and x values, the fluorite cubic structure of pure CeO₂ transforms to a mixture (c′) of the cubic c and tetragonal t″ phases for x = 0.35, and to tetragonal t phase only for x = 0.8 at 650 °C, x = 0.65 at 800 °C, and, to a very limited extent, x = 0.5 at 1000 °C. No evidence is obtained at low x values of the t phase, which is detrimental to the oxygen storage capacity. Prolonged heating at 1000 °C demonstrates that only for x = 0.65 a limited separation of CeO₂‐rich nanocrystals occurs. The samples undergo the same transition without simultaneous occurrence of different phases, apart for the two mentioned limited cases. This result is attributed to the intimate mixing of the metal cations even in the early stages of processing. In as‐prepared samples the Zr distribution becomes inhomogeneous when going from x = 0.2 to x = 0.35, but no early phase separations appear. The oxygen storage capacity is favorably influenced by the persistence of the cubic c′ phase.     

Effect of Ce-Doping on Thermoelectric Properties in PbTe Alloys Prepared by Spark Plasma Sintering

Ce-doped Pb_1−x Ce _x Te alloys with x = 0, 0.005, 0.01, 0.015, 0.03, and 0.05 were prepared by induction melting, ball milling, and spark plasma sintering techniques. The structure and thermoelectric properties of the samples were investigated. X-ray diffraction (XRD) analysis indicated that the samples were of single phase with NaCl-type structure for x less than 0.03. The lattice parameter a increases with increasing Ce content. The lower Ce-doped samples (x = 0.005 and 0.01) showed p-type conduction, whereas the pure PbTe and the higher doped samples (x = 0, 0.015, 0.03, and 0.05) showed n-type conduction. The lower Ce-doped samples exhibited a much higher absolute Seebeck coefficient, but the higher electrical resistivity and higher thermal conductivity compared with pure PbTe resulted in a lower figure of merit ZT. In contrast, the higher Ce-doped samples exhibited a lower electrical resistivity, together with a lower absolute Seebeck coefficient and comparable thermal conductivity, leading to ZT comparable to that of PbTe. The lowest thermal conductivity (range from 0.99 W m⁻¹ K⁻¹ at 300 K to 0.696 W m⁻¹ K⁻¹ at 473 K) was found in the alloy Pb_0.95Ce_0.05Te due to the presence of the secondary phases, leading to a ZT higher than that of pure PbTe above 500 K. The maximum figure of merit ZT, in the alloy Pb_0.95Ce_0.05Te, was 0.88 at 673 K.     

Thermoelectric Properties of (Pb,Sn,Ge)Te-Based Alloys

The search for alternative energy sources is presently at the forefront of␣applied research. In this context, thermoelectricity for direct energy conversion from thermal to electrical energy plays an important role. This␣paper is␣concerned with the development of highly efficient p-type [(PbTe)(SnTe)(Bi₂Te₃)] _x (GeTe)_1−x alloys for thermoelectric applications using spark plasma sintering (SPS). Varying the carrier concentration of GeTe was achieved by alloying of PbTe, SnTe, and/or Bi₂Te₃. The rhombohedral to cubic phase transition temperature, T _c, was found to be sensitive to the degree of alloying. Highest power factor values (P ≤ 33 μW/cm K²) were obtained for (GeTe)_0.95(Bi₂Te₃)_0.05 composition.     

Unveiling the Nanoparticle‐Seeded Catalytic Nucleation Kinetics of Perovskite Solar Cells by Time‐Resolved GIXS

Recently, a new seeding growth approach for perovskite thin films is reported to significantly enhance the device performance of perovskite solar cells. This work unveils the intermediate structures and the corresponding growth kinetics during conversion to perovskite crystal thin films assisted by seeding PbS nanocrystals (NCs), using time‐resolved grazing‐incidence X‐ray scattering. Through analyses of time‐resolved crystal formation kinetics obtained from synchrotron X‐rays with a fast subsecond probing time resolution, an important “catalytic” role of the seed‐like PbS NCs is clearly elucidated. The perovskite precursor‐capped PbS NCs are found to not only accelerate the nucleation of a highly oriented intermediate phase, but also catalyze the conversion of the intermediate phase into perovskite crystals with a reduced activation energy E_a = 47 (±5) kJ mol^?1, compared to 145 (±38) kJ mol^?1 for the pristine perovskite thin film. The reduced E_a is attributed to a designated crystal lattice alignment of the perovskite nanocrystals with perovskite cubic crystals; the pivotal heterointerface alignment of the perovskite crystals coordinated by the Pb NCs leads to an improved film surface morphology with less pinholes and enhanced crystal texture and thermal stability. These together contribute to the significantly improved photovoltaic performance of the corresponding devices.     

Thermoelectric quantum-dot superlattices with high ZT

Following the experimentally observed Seebeck coefficient enhancement in PbTe quantum wells in Pb_1−xEu_xTe/PbTe multiple-quantum-well structures which indicated the potential usefulness of low dimensionality, we have investigated the thermoelectric properties of PbSe_xTe_1−x/PbTe quantum-dot superlattices for possible improved thermoelectric materials. We have again found enhancements in Seebeck coefficient and thermoelectric figure of merit (ZT) relative to bulk values, which occur through the various physics and materials science phenomena associated with the quantum-dot structures. To date, we have obtained estimated ZT values approximately double the best bulk PbTe values, with estimated ZT as high as about 0.9 at 300 K.     

Highly Efficient Ge-Rich Ge<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Pb<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Te Thermoelectric Alloys

The search for alternative energy sources is presently at the forefront of applied research. In this context, thermoelectricity for direct energy conversion from thermal to electrical energy plays an important role. This paper is concerned with the development of highly efficient p-type Ge _x Pb_1−x Te alloys for thermoelectric applications, using spark plasma sintering. The carrier concentration of GeTe was varied by alloying of PbTe and/or by Bi₂Te₃ doping. Very high ZT values up to ~1.8 at 500°C were obtained by doping Pb_0.13Ge_0.87Te with 3 mol% Bi₂Te₃.     

High thermoelectric figures of merit in PbTe quantum wells

High-quality Pb_1−xEu_xTe/PbTe multiple quantum wells (MQWs) have been grown by molecular beam epitaxy. The measured 300K thermoelectric properties have been compared with that of the best bulk PbTe. This experimental investigation is the first detailed study of MQW structures designed to improve ZT of thermoelectric materials and has resulted in a breakthrough in the decades-long ZT ≅ 1 barrier for a room-temperature thermoelectric material. A value of Z_2DT >1.2 has been achieved for these PbTe quantum wells.     

Electronic Structure and Thermoelectric Properties of Al-Mn-Fe-Si Alloys

In order to develop practical thermoelectric materials consisting solely of environmentally friendly elements, we investigated the thermoelectric properties of the Al₁₀Mn₃-type (P6₃/mmc, hp26) Al_77−x Mn₂₃Si _x alloys and the Al₁₀₂Mn₂₄Si₁₂-type (Pm-3, cP138) Al_82−x Mn_5.5Fe_12.5Si _x alloys, both of which possess a pseudogap at the Fermi level. The formation range in which the single phase is obtained was determined for these two phases. The electrical resistivity, Seebeck coefficient, and thermal conductivity of the samples involving no secondary phase were measured over the temperature range of 2 K to 300 K. It is found that the thermoelectric properties of these phases are qualitatively accounted for in terms of the pseudogap at the Fermi level in the electronic density of states and the disordering in local atomic arrangements.     

Synthesis and Thermoelectric Properties of LAST System Bulk Materials: Substitution of Sulfur for Tellurium

Nonstoichiometric lead-antimony-silver-tellurium (LAST) system thermoelectric bulk materials Ag_0.8Pb_22.5SbTe_20?x S _x (x?=?0 to 8.0) were fabricated by combining mechanical alloying (MA) and spark plasma sintering (SPS). The electrical and thermal transport properties were investigated in the temperature range of 300?K to 700?K. The x-ray diffraction (XRD) results indicated that sulfur entered the PbTe during MA process, but gradually precipitated in the sintering process in the form of PbS from the PbTe matrix when the sulfur content was changed from x?=?2.0 to x?=?8.0. It was confirmed that the addition of sulfur effectively reduced the lattice thermal conductivity. A low thermal conductivity of 0.83?W?m^?1?K^?1 at 673?K was obtained for the Ag_0.8Pb_22.5SbTe₁₂S₈ sample. Benefiting from the high electrical conductivity, the Ag_0.8Pb_22.5SbTe₁₈S₂ sample reached a maximum ZT value of ??0.97 at 673?K, which is 32% higher than its counterpart without sulfur substitution.     

Pseudobinary phase diagram and existence regions for PbS1−xSex

The pseudobinary phase diagram of the PbS_1−xSe_x system has been re-determined by using thermal analysis to measure the liquidus temperatures and electron microprobe analysis of the first-to-freeze portions of Bridgman-grown ingots to establish the solidus points. The minimum in the liquidus occurs at x = 0.73 and 1076° C. The separation between our solidus and liquidus curves is considerably less than Simpson reports. For PbS_1=xSe_x alloys with 0. 35 ≼ x≼ 0.41, the existence region between 300 and 800° C has been determined by means of Hall coefficient measurements at 77K on Bridgman-grown crystals that were either Pb-saturated or chalcogen-saturated by isothermal annealing and then quenched. Both the Pb-rich and chalcogen-rich solidus lines are retrograde, and the existence region is nearly symmetrical about the stoichiometric composition. New data for the retrograde S-rich solidus of PbS have also been obtained. This work was sponsored by the Department of the Air Force.