Polycrystalline SnSe with a thermoelectric figure of merit greater than the single crystal.

Thermoelectric materials generate electric energy from waste heat, with conversion efficiency governed by the dimensionless figure of merit, ZT. Single-crystal tin selenide (SnSe) was discovered to exhibit a high ZT of roughly 2.2-2.6 at 913 K, but more practical and deployable polycrystal versions of the same compound suffer from much poorer overall ZT, thereby thwarting prospects for cost-effective lead-free thermoelectrics. The poor polycrystal bulk performance is attributed to traces of tin oxides covering the surface of SnSe powders, which increases thermal conductivity, reduces electrical conductivity and thereby reduces ZT. Here, we report that hole-doped SnSe polycrystalline samples with reagents carefully purified and tin oxides removed exhibit an ZT of roughly 3.1 at 783 K. Its lattice thermal conductivity is ultralow at roughly 0.07 W m-1 K-1 at 783 K, lower than the single crystals. The path to ultrahigh thermoelectric performance in polycrystalline samples is the proper removal of the deleterious thermally conductive oxides from the surface of SnSe grains. These results could open an era of high-performance practical thermoelectrics from this high-performance material.

Exceptionally High Average Power Factor and Thermoelectric Figure of Merit in n-type PbSe by the Dual Incorporation of Cu and Te.

Thermoelectric materials with high average power factor and thermoelectric figure of merit (ZT) has been a sought-after goal. Here, we report new n-type thermoelectric system CuxPbSe0.99Te0.01 (x = 0.0025, 0.004, and 0.005) exhibiting record-high average ZT ∼ 1.3 over 400-773 K ever reported for n-type polycrystalline materials including the state-of-the-art PbTe. We concurrently alloy Te to the PbSe lattice and introduce excess Cu to its interstitial voids. Their resulting strong attraction facilitates charge transfer from Cu atoms to the crystal matrix significantly. It follows the increased carrier concentration without damaging its mobility and the consequently improved electrical conductivity. This interaction also increases effective mass of electron in the conduction band according to DFT calculations, thereby raising the magnitude of Seebeck coefficient without diminishing electrical conductivity. Resultantly, Cu0.005PbSe0.99Te0.01 attains an exceptionally high average power factor of ∼27 µW cm-1 K-2 from 400 to 773 K with a maximum of ∼30 µW cm-1 K-2 at 300 K, the highest among all n- and p-type PbSe-based materials. Its ∼23 µW cm-1 K-2 at 773 K is even higher than ∼21 µW cm-1 K-2 of the state-of-the-art n-type PbTe. Interstitial Cu atoms induce the formation of coherent nanostructures. They are highly mobile, displacing Pb atoms from the ideal octahedral center and severely distorting the local microstructure. This significantly depresses lattice thermal conductivity to ∼0.2 Wm-1 K-1 at 773 K below the theoretical lower bound. The multiple effects of the dual incorporation of Cu and Te synergistically boosts a ZT of Cu0.005PbSe0.99Te0.01 to ∼1.7 at 773 K.

Defect Engineering for High-Performance n-Type PbSe Thermoelectrics.

Introducing structural defects such as vacancies, nanoprecipitates, and dislocations is a proven means of reducing lattice thermal conductivity. However, these defects tend to be detrimental to carrier mobility. Consequently, the overall effects for enhancing ZT are often compromised. Indeed, developing strategies allowing for strong phonon scattering and high carrier mobility at the same time is a prime task in thermoelectrics. Here we present a high-performance thermoelectric system of Pb0.95(Sb0.033□0.017)Se1- yTe y (□ = vacancy; y = 0-0.4) embedded with unique defect architecture. Given the mean free paths of phonons and electrons, we rationally integrate multiple defects that involve point defects, vacancy-driven dense dislocations, and Te-induced nanoprecipitates with different sizes and mass fluctuations. They collectively scatter thermal phonons in a wide range of frequencies to give lattice thermal conductivity of ∼0.4 W m-1 K-1, which approaches to the amorphous limit. Remarkably, Te alloying increases a density of nanoprecipitates that affect mobility negligibly and impede phonons significantly, and it also decreases a density of dislocations that scatter both electrons and phonons heavily. As y is increased to 0.4, electron mobility is enhanced and lattice thermal conductivity is decreased simultaneously. As a result, Pb0.95(Sb0.033□0.017)Se0.6Te0.4 exhibits the highest ZT ∼ 1.5 at 823 K, which is attributed to the markedly enhanced power factor and reduced lattice thermal conductivity, in comparison with a ZT ∼ 0.9 for Pb0.95(Sb0.033□0.017)Se that contains heavy dislocations only. These results highlight the potential of defect engineering to modulate electrical and thermal transport properties independently. We also reveal the defect formation mechanisms for dislocations and nanoprecipitates embedded in Pb0.95(Sb0.033□0.017)Se0.6Te0.4 by atomic resolution spherical aberration-corrected scanning transmission electron microscopy.

High-Performance n-Type PbSe-Cu2Se Thermoelectrics through Conduction Band Engineering and Phonon Softening.

From a structural and economic perspective, tellurium-free PbSe can be an attractive alternative to its more expensive isostructural analogue of PbTe for intermediate temperature power generation. Here we report that PbSe0.998Br0.002-2%Cu2Se exhibits record high peak ZT 1.8 at 723 K and average ZT 1.1 between 300 and 823 K to date for all previously reported n- and p-type PbSe-based materials as well as tellurium-free n-type polycrystalline materials. These even rival the highest reported values for n-type PbTe-based materials. Cu2Se doping not only enhance charge transport properties but also depress thermal conductivity of n-type PbSe. It flattens the edge of the conduction band of PbSe, increases the effective mass of charge carriers, and enlarges the energy band gap, which collectively improve the Seebeck coefficient markedly. This is the first example of manipulating the electronic conduction band to enhance the thermoelectric properties of n-type PbSe. Concurrently, Cu2Se increases the carrier concentration with nearly no loss in carrier mobility, even increasing the electrical conductivity above ∼423 K. The resulting power factor is ultrahigh, reaching ∼21-26 µW cm-1 K-2 over a wide range of temperature from ∼423 to 723 K. Cu2Se doping substantially reduces the lattice thermal conductivity to ∼0.4 W m-1 K-1 at 773 K, approaching its theoretical amorphous limit. According to first-principles calculations, the achieved ultralow value can be attributed to remarkable acoustic phonon softening at the low-frequency region.

Enhancing p-Type Thermoelectric Performances of Polycrystalline SnSe via Tuning Phase Transition Temperature.

SnSe emerges as a new class of thermoelectric materials since the recent discovery of an ultrahigh thermoelectric figure of merit in its single crystals. Achieving such performance in the polycrystalline counterpart is still challenging and requires fundamental understandings of its electrical and thermal transport properties as well as structural chemistry. Here we demonstrate a new strategy of improving conversion efficiency of bulk polycrystalline SnSe thermoelectrics. We show that PbSe alloying decreases the transition temperature between Pnma and Cmcm phases and thereby can serve as a means of controlling its onset temperature. Along with 1% Na doping, delicate control of the alloying fraction markedly enhances electrical conductivity by earlier initiation of bipolar conduction while reducing lattice thermal conductivity by alloy and point defect scattering simultaneously. As a result, a remarkably high peak ZT of ∼1.2 at 773 K as well as average ZT of ∼0.5 from RT to 773 K is achieved for Na0.01(Sn1-xPbx)0.99Se. Surprisingly, spherical-aberration corrected scanning transmission electron microscopic studies reveal that NaySn1-xPbxSe (0 < x ≤ 0.2; y = 0, 0.01) alloys spontaneously form nanoscale particles with a typical size of ∼5-10 nm embedded inside the bulk matrix, rather than solid solutions as previously believed. This unexpected feature results in further reduction in their lattice thermal conductivity.

Fabrication of Bi2Te3-x Se x nanowires with tunable chemical compositions and enhanced thermoelectric properties.

Uniform Bi2Te3-x Se x nanowires (NWs) with tunable components are synthesized by a modified solution method free of any template, and inter-diffusion mechanism is proposed for the growth and transformation of ternary nanowires. Spark plasma sintering is adopted to fabricate the pellets of Bi2Te3-x Se x NWs and thermoelectric transport properties are measured. As compared to Bi2Te3 pellets, Se doping results in lowered electrical conductivity because of the reduced carrier concentration, both the Seebeck coefficient and the power factor are enhanced substantially. The Bi2Te2.7Se0.3 pellet exhibits the highest power factor at room temperature as a result of optimized carrier concentration (4.37 × 1019 cm-3) and mobility (60.22 cm2 V-1 s-1). As compared to Bi2Te3, the thermal conductivity of Bi2Te3-x Se x is lowered owing to the enhanced phonon scattering by dopants and grain boundaries. As a result, the ZT value at 300 K is substantially improved from 0.045 of Bi2Te3 to 0.42 of Bi2Te2.7Se0.3. It is suggested that Se doping is an effective way to enhance the thermoelectric performance of Bi2Te3 based materials.

Heavy-to-light electron transition enabling real-time spectra detection of charged particles by a biocompatible semiconductor.

The current challenge of wearable/implantable personal dosimeters for medical diagnosis and radiotherapy applications is lack of suitable detector materials possessing both excellent detection performance and biocompatibility. Here, we report a solution-grown biocompatible organic single crystalline semiconductor (OSCS), 4-Hydroxyphenylacetic acid (4HPA), achieving real-time spectral detection of charged particles with single-particle sensitivity. Along in-plane direction, two-dimensional anisotropic 4HPA exhibits a large electron drift velocity of 5 × 105 cm s-1 at "radiation-mode" while maintaining a high resistivity of (1.28 ± 0.003) × 1012 Ω·cm at "dark-mode" due to influence of dense π-π overlaps and high-energy L1 level. Therefore, 4HPA detectors exhibit the record spectra detection of charged particles among their organic counterparts, with energy resolution of 36%, (µt)e of (4.91 ± 0.07) × 10-5 cm2 V-1, and detection time down to 3 ms. These detectors also show high X-ray detection sensitivity of 16,612 µC Gyabs-1 cm-3, detection of limit of 20 nGyair s-1, and long-term stability after 690 Gyair irradiation.

Strong charge carrier scattering at grain boundaries of PbTe caused by the collapse of metavalent bonding.

Grain boundaries (GBs) play a significant role in controlling the transport of mass, heat and charge. To unravel the mechanisms underpinning the charge carrier scattering at GBs, correlative microscopy combined with local transport measurements is realized. For the PbTe material, the strength of carrier scattering at GBs depends on its misorientation angle. A concomitant change in the barrier height is observed, significantly increasing from low- to high-angle GBs. Atom probe tomography measurements reveal a disruption of metavalent bonding (MVB) at the dislocation cores of low-angle GBs, as evidenced by the abrupt change in bond-rupture behavior. In contrast, MVB is completely destroyed at high-angle GBs, presumably due to the increased Peierls distortion. The collapse of MVB is accompanied by a breakdown of the dielectric screening, which explains the enlarged GB barrier height. These findings correlate charge carrier scattering with bonding locally, promising new avenues for the design of advanced functional materials.

High-Performance Industrial-Grade CsPbBr3 Single Crystal by Solid-Liquid Interface Engineering.

All-inorganic metal halide perovskite CsPbBr3 crystal is regarded as an attractive alternative to high purity Ge and CdZnTe for room temperature γ-ray detection. However, high γ-ray resolution is only observable in small CsPbBr3 crystal; more practical and deployable large crystal exhibits very low, and even no detection efficiency, thereby thwarting prospects for cost-effective room temperature γ-ray detection. The poor performance of large crystal is attributed to the unexpected secondary phase inclusion during crystal growth, which traps the generated carriers. Here, the solid-liquid interface during crystal growth is engineered by optimizing the temperature gradient and growth velocity. This minimizes the unfavorable formation of the secondary phase, leading to industrial-grade crystals with a diameter of 30 mm. This excellent-quality crystal exhibits remarkably high carrier mobility of 35.4 cm2 V-1 s-1 and resolves the peak of 137 Cs@ 662 keV γ-ray at an energy resolution of 9.91%. These values are the highest among previously reported large crystals.

Doping by Design: Enhanced Thermoelectric Performance of GeSe Alloys Through Metavalent Bonding.

Doping is usually the first step to tailor thermoelectrics. It enables precise control of the charge-carrier concentration and concomitant transport properties. Doping should also turn GeSe, which features an intrinsically a low carrier concentration, into a competitive thermoelectric. Yet, elemental doping fails to improve the carrier concentration. In contrast, alloying with Ag-V-VI2 compounds causes a remarkable enhancement of thermoelectric performance. This advance is closely related to a transition in the bonding mechanism, as evidenced by sudden changes in the optical dielectric constant ε∞ , the Born effective charge, the maximum of the optical absorption ε2 (ω), and the bond-breaking behavior. These property changes are indicative of the formation of metavalent bonding (MVB), leading to an octahedral-like atomic arrangement. MVB is accompanied by a thermoelectric-favorable band structure featuring anisotropic bands with small effective masses and a large degeneracy. A quantum-mechanical map, which distinguishes different types of chemical bonding, reveals that orthorhombic GeSe employs covalent bonding, while rhombohedral and cubic GeSe utilize MVB. The transition from covalent to MVB goes along with a pronounced improvement in thermoelectric performance. The failure or success of different dopants can be explained by this concept, which redefines doping rules and provides a "treasure map" to tailor p-bonded chalcogenides.

[The relationship between hypoxia-inducible factor-1α and cartilage degeneration in osteoarthritis: a review].

Osteoarthritis is one of the most common diseases seen in clinical practice. Cartilage survives in the hypoxic microenvironment. Hypoxia-inducible factor-1α (HIF-1α) is a key nuclear transcription factor which mediates the hypoxic response of cells. HIF-1α gene is an important regulator for the adaptation of articular cartilage to the hypoxic environment. It is important for formation of articular cartilage, energy metabolism and matrix synthesis. If the HIF-1α gene is knocked out, the cartilage can not maintain their normal morphology and function, which may lead to cartilage degeneration, and result in diseases such as osteoarthritis. Chinese herbal medicines can regulate the expression of HIF-1α gene and supply a therapy method for osteoarthritis. In this paper, the authors review the situation of the correlation between HIF-1α and osteoarthritis cartilage degeneration examined in recent years.

[Professor Shi Qi's experience of applying herbal paste for treating chronic musculoskeletal conditions].

Professor Shi Qi is a famous traditional Chinese medicine doctor specializing in orthopaedics and traumatology, who has formatted a set of systematic protocols for the diagnosis and treatment of chronic musculoskeletal conditions. When it is time for using tonics in winter, he advocates applying herbal paste for treating chronic musculoskeletal diseases. This paper introduces Professor Shi Qi's commonly used prescription for treating chronic musculoskeletal conditions and puts forward demands and understandings in concocting herbal paste, experience in herbal paste for treating chronic musculoskeletal diseases such as cervical spondylosis, lumbar disc herniation, lumbar spinal stenosis, lumbar muscle strain, ankylosing spondylitis, osteoporosis, knee osteoarthritis and avascular necrosis of femoral head, and the advantages of herbal paste for treating chronic musculoskeletal conditions as opposed to alternative treatments.

Atomic Level Defect Structure Engineering for Unusually High Average Thermoelectric Figure of Merit in n-Type PbSe Rivalling PbTe.

Realizing high average thermoelectric figure of merit (ZTave ) and power factor (PFave ) has been the utmost task in thermoelectrics. Here the new strategy to independently improve constituent factors in ZT is reported, giving exceptionally high ZTave and PFave in n-type PbSe. The nonstoichiometric, alloyed composition and resulting defect structures in new Pb1+ x Se0.8 Te0.2 (x = 0-0.125) system is key to this achievement. First, incorporating excess Pb unusually increases carrier mobility (µH ) and concentration (nH ) simultaneously in contrast to the general physics rule, thereby raising electrical conductivity (σ). Second, modifying charge scattering mechanism by the authors' synthesis process boosts a magnitude of Seebeck coefficient (S) above theoretical expectations. Detouring the innate inverse proportionality between nH and µH ; and σ and S enables independent control over them and change the typical trend of PF to temperature, giving remarkably high PFave ≈20 µW cm-1 K-2 from 300 to 823 K. The dual incorporation of Te and excess Pb generates unusual antisite Pb at the anionic site and displaced Pb from the ideal position, consequently suppressing lattice thermal conductivity. The best composition exhibits a ZTave of ≈1.2 from 400 to 823 K, one of the highest reported for all n-type PbQ (Q = chalcogens) materials.

Inhibitory effect of YQHYRJ recipe on osteoblast differentiation induced by BMP-2 in fibroblasts from posterior longitudinal ligament of mice.

Ossification of posterior longitudinal ligament (OPLL) is a common disease in Asian countries. Osteoblast differentiation in posterior longitudinal ligamentous fibroblast is a pathologic basis of OPLL. Nowadays, an effective pharmacotherapy for OPLL is still hunted for. YQHYRJ Recipe (YQHYRJ) is designed based on traditional Chinese medicine (TCM) theories, and previous clinic trials reported its effect on relieving syndromes of cervical spondylopathy. To clarify the YQHYRJ effect of OPLL on a cellular level, we induced mice fibroblasts from posterior longitudinal ligaments to differentiate into osteoblasts by human recombinant BMP-2, and treated them with YQHYRJ and its three sub-compounds: YQ, HY and RJ. YQHYRJ and the sub-compounds reduced the increase of fibroblast proliferation, mineralization, type I collagen secretion induced by BMP-2 via MTT, alizarin red staining and immunochemical examination. Moreover, these agents inhibited BMP-2 induced upregulation of ossification-related genes ALP, Col I and OC as well as BMP signal molecules Smad1, Smad 5 and Runx2 mRNA expression. These results suggested YQHYRJ to be effective in inhibiting osteoblast differentiation induced by BMP-2 in fibroblasts from posterior longitudinal ligament. YQHYRJ might be a promising medicine for preventing OPLL disease.

[Effects of Chinese herbal medicine Yiqi Huayu Recipe on apoptosis of dorsal root ganglion neurons and expression of caspase-3 in rats with lumbar nerve root compression].

OBJECTIVE: To observe the effects of Yiqi Huayu Recipe, a Chinese compound herbal medicine, on apoptosis of dorsal root ganglion (DRG) neurons and expression of caspase-3 in rats after lumbar nerve root compression injury. METHODS: A total of 40 male Sprague-Dawley rats were randomly allocated into 4 groups: control group, untreated group, Methylcobal group and Yiqi Huayu Recipe group. Surgery was performed on rats of untreated group, Methylcobal group and Yiqi Huayu Recipe group to place a micro-silica gel on right L4 DRG, while control group received skin and paravertebral muscle incision only. Rats in Methylcobal group and Yiqi Huayu Recipe group were given Methylcobal by intramuscular injection and Yiqi Huayu Recipe intragastrically respectively. Rats in control group and untreated group received saline intragastrically as equal amount as Yiqi Huayu Recipe group. The compressed nerve roots were harvested at the 10th day after treatment. Apoptosis of DRG neurons was detected by terminal deoxynucleotidyl transferase-mediated nick-end labeling. Caspase-3 activity and mRNA expression in compressed nerve roots were detected with spectrophotography and real-time polymerase chain reaction respectively. RESULTS: Apoptosis of DRG neurons was significantly increased in the rat model. The apoptosis index of untreated group was higher than that of control group (P<0.01). Yiqi Huayu Recipe and Methylcobal could reduce the apoptosis of DRG neurons, and both groups showed a lower apoptosis index than untreated group (P<0.01). Caspase-3 activity and its gene expression were significantly increased in untreated group. The levels of caspase-3 activity and its gene expression in untreated group were higher than those in control group (P<0.05 or P<0.01). Yiqi Huayu Recipe and Methylcobal could reduce the overexpression of caspase-3 mRNA, and statistically significant differences were found between the untreated group and Yiqi Huayu Recipe group or Methylcobal group (P<0.01). CONCLUSION: Lumbar nerve root compression results in overexpression of caspase-3 in nerve root tissue and increase of DRG neuron apoptosis. Yiqi Huayu Recipe can inhibit the overexpression of caspase-3 and alleviate the apoptosis of DRG neurons after nerve injury.

[Effects of Yiqi Huayu Decoction on brain-derived neurotrophic factor expression in rats with lumbar nerve root injury].

OBJECTIVE: To observe the effects of Yiqi Huayu Decoction, a compound traditional Chinese herbal medicine, on brain-derived neurotrophic factor (BDNF) expression in lumbar nerve root and soleus of rats after lumbar nerve root compression injury. METHODS: A total of 120 male SD rats were randomly allocated into sham-operated group, untreated group, methycobal injection group and Yiqi Huayu Decoction group. Surgery were performed on rats of untreated group, methycobal injection group and Yiqi Huayu Decoction group by placing a micro-silica gel on right L(4) dorsal root ganglia, while rats in sham-operated group received skin and paravertebral muscle incision only. Rats in the methycobal injection group and the Yiqi Huayu Decoction group were given intramuscular injection of methycobal and intragastric administration of Yiqi Huayu Decoction respectively. Rats in the sham-operated group and the untreated group received intragastric administration of normal saline of equal volume as Yiqi Huayu Decoction. The compressed nerve roots and right soleus were harvested after 10-, 30- and 60-day treatment. Microstructure of the compressed nerve roots were revealed under a transmission electron microscope. BDNF protein expression in the compressed nerve roots and mRNA expression in right solues were detected with enzyme-linked immunosorbent assay (ELISA) and real-time quantitative reverse transcription-polymerase chain reaction respectively. RESULTS: The protein expression level of BDNF in compressed nerve root in the untreated group was slightly changed with no significance as compared with sham-operated group. BDNF protein expression in the Yiqi Huayu Decoction group was gradually increased and reached the peak level after 60-day treatment with significant difference as compared with the untreated group (P<.01). The expression of BDNF mRNA in soleus was significantly up-regulated 10 days after nerve root injury (P<0.01), and was slowly decreased to the normal level at day 60 (P>0.05). Compared with the untreated group, BDNF mRNA expression in soleus muscle in the Yiqi Huayu Decoction group was significantly down-regulated after 10-day treatment (P<0.01), while was increased after 60-day treatment (P<0.01). CONCLUSION: Yiqi Huayu Decoction can inhibit the increase of BDNF expression at the early phase after nerve injury, which may have something to do with alleviation of neuropathic pain, and increase BDNF expression at the late phase to promote nerve regeneration.

[Mechanism of Yiqi Huayu Bushen recipe in treating cervical syndrome in rats with qi deficiency, blood stasis and kidney deficiency].

OBJECTIVE: To explore the mechanism of Yiqi Huayu Bushen Recipe (YHBR), a compound traditional Chinese herbal medicine, in treating cervical syndrome (CS) with qi deficiency, blood stasis and kidney deficiency in rats. METHODS: A total of 30 three-month-old female Sprague-Dawley rats were randomly divided into normal control group, untreated group and YHBR group; there were ten rats in each group. The rat model of cervical syndrome with qi deficiency, blood stasis and kidney deficiency was established by combining disease and syndrome models. After one-month YHBR treatment in YHBR group, all rats were sacrificed. Serum, plasma and cervical intervertebral discs were detected and observed by radio-immunology, histopathology, immunohistochemistry, etc. RESULTS: Compared with those in the normal control group, rats in the untreated group showed obvious signs of deficiency in vital energy, such as tiredness, ptosis, few movement, bluish-purple tongue and tail and weight loss; the weight of uterus and appendages, and the ratio of cyclic adenosine monophosphate/cyclic guanosine monophosphate were decreased; hemorheological parameters and the expression of alpha-granular membrane protein (CD62p) were increased; the content of serum estradiol was decreased. YHBR could improve the above indexes except for the weight of uterus and appendages. HE staining showed annulus fibrosus with cracks, diminish of pulposus nucleus, and decrease in the height of intervertebral disc and the thickness of end-plate in the untreated group; and YHBR could improve the changes of cervical intervertebral discs, but no obvious changes in end-plate. Type II collagen protein (Col2a1)was distributed in every part of the annulus fibrosus in normal control group, but was decreased in untreated group; YHBR could increase Col2a1 expression in annulus fibrosus as compared with the untreated group. The expressions of Col2a1 and tissue inhibitor of metalloproteinase-1 (TIMP-1) mRNAs were decreased in untreated group as compared with the normal control group (P<0.01); the expressions of Col2a1 and TIMP-1 mRNAs were higher and matrix metalloproteinase-13 mRNA was lower in the YHBR group than those in the untreated group (P<0.05, P<0.01). CONCLUSION: YHBR may improve the condition of cervical syndrome with qi deficiency, blood stasis and kidney deficiency by regulating immune system, coagulation system and endocrine system, and delay the degeneration of cervical intervertebral disc by regulating extracellular matrix and metalloproteases in intervertebral disc.

Ultrahigh Power Factor and Electron Mobility in n-Type Bi2Te3-x%Cu Stabilized under Excess Te Condition.

The thermoelectric (TE) community has mainly focused on improving the figure of merit (ZT) of materials. However, the output power of TE devices directly depends on the power factor (PF) rather than ZT. Effective strategies of enhancing PF have been elusive for Bi2Te3-based compounds, which are efficient thermoelectrics operating near ambient temperature. Here, we report ultrahigh carrier mobility of ∼467 cm2 V-1 s-1 and power factor of ∼45 µW cm-1 K-2 in a new n-type Bi2Te3 system with nominal composition CuxBi2Te3.17 (x = 0.02, 0.04, and 0.06). It is obtained by reacting Bi2Te3 with surplus Cu and Te and subsequently pressing powder products by spark plasma sintering (SPS). The SPS discharges excess Te but stabilizes the high extent of Cu in the structure, giving unique SPS CuxBi2Te3.17 samples. The analyzed composition is close to "CuxBi2Te3". Their charge transport properties are highly unusual. Hall carrier concentration and mobility simultaneously increase with the higher mole fraction of Cu contrary to the typical carrier scattering mechanism. As a consequence, the electrical conductivity is considerably enhanced with Cu incorporation. The Seebeck coefficient is nearly unchanged by the increasing Cu content in contrast to the general understanding of inverse relationship between electrical conductivity and Seebeck coefficient. These effects synergistically lead to a record high power factor among all polycrystalline n-type Bi2Te3-based materials.

High Thermoelectric Performance in n-Type Polycrystalline SnSe via Dual Incorporation of Cl and PbSe and Dense Nanostructures.

Despite extensive studies on emerging thermoelectric material SnSe, its n-type form is largely underdeveloped mainly due to the difficulty in stabilizing the carrier concentration at the optimal level. Here, we dually introduce Cl and PbSe to induce n-type conduction in intrinsic p-type SnSe. PbSe alloying enhances the power factor and suppresses lattice thermal conductivity at the same time, giving a highest thermoelectric figure of merit ZT of 1.2 at 823 K for n-type polycrystalline SnSe materials. The best composition is Sn0.90Pb0.15Se0.95Cl0.05. Samples prepared by the solid-state reaction show a high maximum ZT ( ZTmax) ∼1.1 and ∼0.8 parallel and perpendicular to the press direction of spark plasma sintering, respectively. Remarkably, post-ball milling and annealing processes considerably reduce structural anisotropy, thereby leading to a ZTmax ∼1.2 along both the directions. Hence, the direction giving a ZTmax is controllable for this system using the specialized preparation methods for specimens. Spherical aberration-corrected scanning transmission electron microscopic analyses reveal the presence of heavily dense edge dislocations and strain fields, not observed in the p-type counterparts, which contribute to decreasing lattice thermal conductivity. Our theoretical calculations employing a Callaway-Debye model support the experimental results for thermal transport and microscopic structures.

Design of Domain Structure and Realization of Ultralow Thermal Conductivity for Record-High Thermoelectric Performance in Chalcopyrite.

Chalcopyrite compound CuGaTe2 is the focus of much research interest due to its high power factor. However, its high intrinsic lattice thermal conductivity seriously impedes the promotion of its thermoelectric performance. Here, it is shown that through alloying of isoelectronic elements In and Ag in CuGaTe2 , a quinary alloy compound system Cu1- x Agx Ga0.4 In0.6 Te2 (0 ≤ x ≤ 0.4) with complex nanosized strain domain structure is prepared. Due to strong phonon scattering mainly by this domain structure, thermal conductivity (at 300 K) drops from 6.1 W m-1 K-1 for the host compound to 1.5 W m-1 K-1 for the sample with x = 0.4. As a result, the optimized chalcopyrite sample Cu0.7 Ag0.3 Ga0.4 In0.6 Te2 presents an outstanding performance, with record-high figure of merit (ZT) reaching 1.64 (at 873 K) and average ZT reaching 0.73 (between ≈300 and 873 K), which are ≈37 and ≈35% larger than the corresponding values for pristine CuGaTe2 , respectively, demonstrating that such domain structure arising from isoelectronic multielement alloying in chalcopyrite compound can effectively suppress its thermal conductivity and elevate its thermoelectric performance remarkably.