P-type Bi0 Research Articles

Effect of Starting Powder Particle Size on the Thermoelectric Properties of Hot-Pressed Bi0.3Sb1.7Te3 Alloys.

P-type Bi0.3Sb1.7Te3 polycrystalline pellets were fabricated using different methods: melting and mechanical alloying, followed by hot-press sintering. The effect of starting powder particle size on the thermoelectric properties was investigated in samples prepared using powders of different particle sizes (with micro- and/or nano-scale dimensions). A peak ZT (350 K) of ~1.13 was recorded for hot-pressed samples prepared from mechanical alloyed powder. Moreover, hot-pressed samples prepared from ≤45 μm powder exhibited similar ZT (~1.1). These high ZT values are attributed both to the presence of high-density grain boundaries, which reduced the lattice thermal conductivity, as well as the formation of antisite defects during milling and grinding, which resulted in lower carrier concentrations and higher Seebeck coefficient values. In addition, Bi0.3Sb1.7Te3 bulk nanocomposites were fabricated in an attempt to further reduce the lattice thermal conductivity. Surprisingly, however, the lattice thermal conductivity showed an unexpected increasing trend in nanocomposite samples. This surprising observation can be attributed to a possible overestimation of the lattice thermal conductivity component by using the conventional Wiedemann-Franz law to estimate the electronic thermal conductivity component, which is known to occur in nanocomposite materials with significant grain boundary electrical resistance.

Uncovering the crystallography and formation mechanism of nanoscale clusters in Sb-rich SPPs of a p-type (Bi, Sb)2Te3 alloy.

Considering that the crystallographic characteristics of the Sb-rich secondary phase particles (SPPs) greatly affect the thermoelectric properties of Bi2Te3 based materials, it is of great significance to explore the mechanism behind the Sb-rich SPPs in the p-type (Bi, Sb)2Te3 material. Here a conventional TEM technique was used to characterize the composition, size and distribution of Sb-rich SPPs in a spark plasma sintered p-type (Bi, Sb)2Te3 alloy. The results indicated that two different morphologies of Sb-rich SPPs including elongated and circular Sb-rich SPPs were frequently observed. Combined with high-resolution transmission electron microscopy, this work provides atomic-scale evidence for the formation mechanism behind the Sb-rich SPPs in the (Bi, Sb)2Te3 material.

Largely enhanced thermoelectric performance in p-type Bi2Te3-based materials through entropy engineering

Entropy optimized Bi2Te3 based materials achieved a high thermoelectric performance with a figure of merit of 1.7 at 450 K and a maximum conversion efficiency of 8% with a temperature gradient of 225 K.

High density lath twins lead to high thermoelectric conversion efficiency in Bi2Te3 modules.

Thermoelectric (TE) generators based on bismuth telluride (Bi2Te3) are recognized as a credible solution for low-grade heat harvesting. In this study, an combinative doping strategy of both the donor (Ag) and the acceptor (Ga) in Ag9GaTe6 as dopants is developed to modulate the microstructure and improve the ZT value of p-type Bi0.4Sb1.6Te3. Specifically, the distribution of Ag and Ga in the matrix synergistically introduces multiple phonon scattering centers including lath twins, triple junction boundaries, and Sb-rich nanoprecipitates, leading to an obviously suppressed lattice thermal conductivity of 0.50 W m-1 K-1 at 300 K. At the same time, such unique microstructures of lath twins synergistically enhance the room-temperature power factor to 48.8 μW cm-1 K-2 and improve the Vickers hardness to 0.90 GPa. Consequently, a high ZT of 1.40 at 350 K and ZTave of 1.24 (300-500 K) are achieved in the Bi0.4Sb1.6Te3 + 0.03 wt% Ag9GaTe6 sample. Based on that, a competitive conversion efficiency of 6.5% at ΔT = 200 K is obtained in the constructed 17-couple TE module, which exhibits no significant change in the output property after 30 thermal cycle tests benefiting from the stable microstructure.

Output performance improvement for thermoelectric transistor with the consideration of the Thomson effect and geometry optimization

Despite significant attention paid to thermoelectric generators in the energy conversion field, their limited output performance has restricted their large-scale applications. Therefore, there is a pressing need to conceive a novel thermoelectric device concept that can strengthen their competitiveness. In this context, the concept and principle of thermoelectric (TE) transistor with ultrahigh performance is a demand-driven innovation. Built on the foundation of a PNP structure, TE transistor only relies on the Seebeck voltage to operate normally. This work employs P-type Bi0.5Sb1.5Te3 and N-type Bi2Te2.97Se0.03 as the component materials. By considering the conduction heat, Joule heat, Thomson heat, and temperature-dependent material properties, a one-dimensional heat transfer model was used to obtain the nonlinear temperature profile inside TE transistor. Further, the structure and operation conditions of TE transistor with varying geometric dimensions were determined based on the hole concentration distribution and build-in voltage variation. Finally, the optimal concentrations and geometric dimensions of TE transistor were obtained using a compromise method. The calculation results reveal that TE transistor can achieve an optimal output power of 133.7 mW under a temperature difference of 50 K (Th = 353 K, Tc = 303 K) with the corresponding conversion efficiency of 7.73%. This work provides theoretical guidance for future experimental validation of TE transistor.

High Thermoelectric Performance Related to PVDF Ferroelectric Domains in P-Type Flexible PVDF-Bi0.5Sb1.5Te3 Composite Film.

There is increasing demand to power Internet of Things devices using ambient energy sources. Flexible, low-temperature, organic/inorganic thermoelectric devices are a breakthrough next-generation approach to meet this challenge. However, these systems suffer from poor performance and expensive processing preventing wide application of the technology. In this study, by combining a ferroelectric polymer (Polyvinylidene fluoride (PVDF, β phase)) with p-type Bi0.5Sb1.5Te3 (BST) a thermoelectric composite film with maximum is produced power factor. Energy filter from ferroelectric-thermoelectric junction also leads to high Seebeck voltage ≈242µVK-1. For the first time, compelling evidence is provided that the dipole of a ferroelectric material is helping decouple electron transport related to carrier mobility and the Seebeck coefficient, to provide 5× or more improvement in thermoelectric power factor. The best composition, PVDF/BST film with BST 95wt.% has a power factor of 712µW•m-1K-2. A thermoelectric generator fabricated from a PVDF/BST film demonstrated Pmax T 12.02µW and Pdensity 40.8Wm-2 under 50K temperature difference. This development also provides a new insight into a physical technique, applicable to both flexible and non-flexible thermoelectrics, to obtain comprehensive thermoelectric performance.

Hierarchical Phonon Scattering from Nano to Macro Scale in Ag-Nano/TiO2-Micro Particle-Decorated p-type Bismuth Telluride Bulk Composites.

We study the thermoelectric properties of a p-type Bi0.4Sb1.6Te3.4 (BST) composite with Ag nanoparticle-decorated TiO2 microparticles (US-Ag/TiO2). The dispersion of US-Ag/TiO2 particles, synthesized by an ultrasonication (US) method, into the matrix effectively decreases lattice and bipolar thermal conductivity, attributed to the scattering centers formed at nano and micro scales. The electron backscattering diffraction (EBSD) measurements revealed smaller grain sizes within the BST composite when paired with the US-Ag/TiO2 particle dispersion. These reduced grain sizes, alongside nanoparticle-decorated microparticles dispersed throughout the matrix, scatter phonons effectively from long- to short-wavelength phonons and subsequently decrease lattice thermal conductivity. While the power factors of the composites are reduced, significant suppression of lattice and bipolar thermal conductivity has led to an increase in the maximum zT value (1.4 at 325 K) for a 0.9 wt % US-Ag/TiO2 particle dispersion within the BST matrix. This particle dispersion in the BST composite consistently demonstrates a high zT value across an extensive temperature spectrum, leading to an exceptionally high average zTavg value (1.38 up to 400 K), which is superior to the other values from reported BST composites. Thus, this research indicates that the dispersion of nanoparticle-decorated microparticles within a thermoelectric material matrix can significantly improve thermoelectric performance, which has promising implications for practical applications in thermoelectric cooling and sustainable and economical energy harvesting technologies.

Transitional structure of {0001} twin in a deformed p-type (Bi,Sb)2Te3 alloy: a direct experimental basis for understanding the twinning mechanism.

Twin boundaries provide a strong phonon scattering center to hinder the lattice thermal conductivity in thermoelectric materials, but the underlying evolution process of deformation twinning remains to be figured out. By applying atomic resolution transmission electron microscope (TEM) observations, a novel type of transitional structure of {0001} twin was observed, for the first time, in the p-type (Bi,Sb)2Te3 alloy subjected to three-point bending deformation. The transformation from matrix to (0001) twin can be realized by the following path: matrix → transitional twin → (0001) twin, and this process was completed by the gliding of a total of four partial dislocations (b1 = 1/3[011̄0]) extended in the different (0001) planes. This new finding here will shed light on the nucleation and growth of deformation twins in the p-type (Bi, Sb)2Te3 alloy.

Lattice distortion of a (0001) twin constrained by grain boundaries in a p-type (bi,Sb)2Te3 alloy during three point bending deformation

Twinning, which is directly related to partial dislocation, has been extensively observed as a main plastic deformation mechanism in crystals. Generally, there are no other lattice defects inside the twins. By using transmission electron microscopy (TEM), we document, for the first time, the presence of lattice distortion of a (0001) twin within a deformed p-type (Bi,Sb)2Te3 alloy. Atomic scale analyses for the characteristics and mechanism of this lattice distortion of a (0001) twin have been systematically carried out with high resolution TEM (HRTEM) and geometric phase analysis (GPA) tool. Results reveal that the mechanism of lattice distortion of a (0001) twin can be attributed to the twisting deformation occurred near the twin boundaries under the effect of an external torque. Further, we constructed structure models of the lattice distortion of a (0001) twin based on HRTEM and GPA analysis.

Extremely Low Contact Resistivity of Bi2Te3-Based Modules Enabled by NiP-Based Alloy Barrier.

Electrode diffusion barrier plays an important role in thermoelectric cooling devices. Compared with p-type Bi0.5Sb1.5Te3, the compatibility between commercial Ni barrier and n-type Bi2Te2.7Se0.3 is a key bottleneck to enhance the performance of Bi2Te3-based cooling devices. This paper proposed a NiP alloy barrier to improve the compatibility with n-type Bi2Te2.7Se0.3, and systemically investigated the contact and interfacial dynamics properties. Due to the low diffusion rate of NiP alloy, the initial interfacial contact resistivity of Bi2Te2.7Se0.3/NiP is as low as 0.90 μΩ cm2, and it further can be depressed below 1.98 μΩ cm2 even after aging at 423 K for 35 days, indicating the superior thermal stability of the NiP barrier layer compared to the commercial Ni barrier layer. Based on the NiP barrier, a 15-pair bismuth telluride device is prepared and a high cooling temperature difference of 71.5 K at a hot-side temperature of 304 K is achieved, which proves the practical applications potential of NiP barrier for Bi2Te3-based modules.

Enhancing conductivity on p-type (Bi,Sb)2Te3 surface by introducing slip trace

Structural modification can effectively tune and optimize the thermoelectric properties of Bi2Te3-based alloys. Herein, we present an innovative and controllable approach to enhance the conductivity of the Bi2Te3-based alloy by introducing slip traces. The effect of slip traces on the conductivity of the Bi2Te3-based alloy was comprehensively investigated using advanced techniques such as Electron Backscatter Diffraction (EBSD) and conductive Atomic Force Microscopy (c-AFM). The results revealed that slip traces were readily formed in (Bi,Sb)2Te3 grains when a load was applied perpendicular to the prismatic plane. The Point Discharge Effect (PDE) was found to promote carriers moving towards the slip traces, leading to the accumulation of positively charged holes. As a result of this process, a higher current intensity was detected at the slip traces. This innovative strategy offers a convenient and effective way to fabricate high-conductivity thermoelectric materials and thus will inspire new technological possibilities for high-performance thermoelectric devices.

Enhanced Thermoelectric Performance of P-Type (Bi,Sb)2 Te3 by Incorporating Non-Stoichiometric Ag5 Te3 and Refining Te-Se Ratio.

Power generation modules utilizing thermoelectric (TE) materials are suitable for recycling widespread low-grade waste heat (<600K), highlighting the immediate necessity for advanced Bi2 Te3 -based alloys. Herein, the substantial enhancement in TE performance of the p-type Bi0.4 Sb1.6 Te3 (BST) sintered sample is realized by subtly incorporating the non-stoichiometric Ag5 Te3 and counteractive Se. Specifically, Ag atoms diffused into the BST lattice improve the density-of-states effective mass (md * ) and boost the hole concentration for the suppressed bipolar effect. The addition of Se further improves md * prompting the room-temperature power factor upgrade to 46Wcm-1 K-2 . Concurrently, the lattice thermal conductivity is considerably lowered by multiple scattering sources exemplified by Sb-rich nanoprecipitates and dense dislocations. These synergistic results yield a high peak ZT of 1.44 at 375K and an average ZT of 1.28 between 300 and 500K in the Bi0.4 Sb1.6 Te2.95 Se0.05 + 0.05wt.% Ag5 Te3 sample. More significantly, when coupled with n-type zone-melted Bi2 Te2.7 Se0.3 , the integrated 17-pair TE module achieves a competitive conversion efficiency of 6.1% and an output power density of 0.40Wcm-2 at a temperature difference of 200K, demonstrating great potential for practical applications.

Large Mobility Enables Higher Thermoelectric Cooling and Power Generation Performance in n-type AgPb18+xSbTe20 Crystals.

The room-temperature thermoelectric performance of materials underpins their thermoelectric cooling ability. Carrier mobility plays a significant role in the electronic transport property of materials, especially near room temperature, which can be optimized by proper composition control and growing crystals. Here, we grow Pb-compensated AgPb18+xSbTe20 crystals using a vertical Bridgman method. A large weighted mobility of ∼410 cm2 V-1 s-1 is achieved in the AgPb18.4SbTe20 crystal, which is almost 4 times higher than that of the polycrystalline counterpart due to the elimination of grain boundaries and Ag-rich dislocations verified by atom probe tomography, highlighting the significant benefit of growing crystals for low-temperature thermoelectrics. Due to the largely promoted weighted mobility, we achieve a high power factor of ∼37.8 μW cm-1 K-2 and a large figure of merit ZT of ∼0.6 in AgPb18.4SbTe20 crystal at 303 K. We further designed a 7-pair thermoelectric module using this n-type crystal and a commercial p-type (Bi, Sb)2Te3-based material. As a result, a high cooling temperature difference (ΔT) of ∼42.7 K and a power generation efficiency of ∼3.7% are achieved, revealing promising thermoelectric applications for PbTe-based materials near room temperature.

Deformation behavior and mechanism of p-type (Bi,Sb)2Te3 alloy during three-point bending test at room temperature

In order to improve the machining process to engineer microstructure and defect types so as to further enhance the thermoelectric properties, it is desirable to understand the deformation behavior and mechanism of polycrystalline Bi2Te3 alloys. This work investigated the deformation behavior and mechanism of (Bi,Sb)2Te3 alloy during three-point bending tests using electron backscatter diffraction (EBSD). Results indicated that both dislocation slip and twinning occurred during the bending tests. The twins with the twin orientation relationship of (0001)M//(0001)T were observed. In addition, the nano-grains extruded the coarse grains in such a way that coarse grains assumed an orientation vulnerable to fracture along the basal planes. Slip trace analysis revealed that 13<112¯0> dislocation slipping on basal planes broke the Van der Waals bonds between the basal planes which eventually led grains to fracture. Additionally, a novel model was introduced that first incorporated the bending moment diagram in order to deduce the deformation process.

Enhancing power generation sustainability of thermoelectric pillars by suppressing diffusion at Bi-Sb-Te/Sn electrode interface using crystalline Co-P coatings

Bismuth telluride-based thermoelectric (TE) devices were widely used in waste heat recovery due to their high thermoelectric figure of merit (ZT), but the severe diffusion between Sn-based solder and TE pillar generated porous and brittle Sn-Te intermetallic compound (IMC), which seriously restricted the reliable service of devices. Ni-based coating was used but the thick Ni-Te IMC also impaired the properties of TE pillars. In this work, the crystalline Co-P coating was inserted between the p-type TE material Bi0.5Sb1.5Te3 and the solder by electrodeposition, and the power generation sustainability of the TE pillar were significantly improved, and the mechanism was revealed. The microstructural characterization proved that the Co-P coating could effectively resist the diffusion of active Sn, Bi, Sb, Cu atoms. Co-P coating would provide support for the structural integrity and performance sustainability of TE pillars. It was worth noting that an ultrathin CoTe2 IMC layer was formed between the Co-P coating and the Bi-Sb-Te pillar, which was much thinner than the Ni-Te IMC layer reported in the literature. This indicated that Co-P only consumed little thermoelectric elements, but also a good metallurgical bond was formed between the Co-P and the Bi-Sb-Te. After aging at 423 K for 150 h, the maximum output power and average Seebeck coefficient of the TE pillar without coating dropped significantly by 74% and 34%, respectively, and the internal resistance rose by 67%. Remarkably, the maximum output power and average Seebeck coefficient of the TE pillar protected by the Co-P coating only decreased by 14% and 5%, respectively, and the internal resistance only increased by 6%.

Controlling the shape of hexagonal structure by growth condition improves the thermoelectric properties of p-type Bi-Te films

Improving the thermoelectric (TE) properties of typical p-type Bi0.5Sb1.5Te3 film is crucial for power generation in film-based thermoelectric devices. The shape of the hexagonal structure in the Bi0.5Sb1.5Te3 film can be controlled by adjusting the magnetron sputtering parameters. The results indicate that a high nucleation rate under high sputtering power promotes island growth with a preferred orientation of (015). Thermal energy influences the growth in the in-plane direction along the (00 l) orientation and induces the c-axis orientation in the out-of-plane direction. Consequently, a dense layered hexagonal structure with a high grain boundary density is formed, leading to increased defect density, carrier concentration, and phonon scattering. In this case, the power factor reaches 3149.01 μW·m-1·K-2 at 480 K and the ZT value is 1.14 at 480 K. These results indicate that the film with a dense layered hexagonal structure enhances the TE properties.

Complex microstructure induced high thermoelectric performances of p-type Bi–Sb–Te alloys

In this research, we have fabricated the complex microstructure features along with the high density of twin boundaries using the combination of magnetic pulse compaction (MPC) and spark plasma sintering (SPS), which are exclusively improved the thermoelectric transport properties of p-type Bi0.5Sb1.5Te3 alloys via effective scattering of carriers and phonons at the grain boundary interfaces. The texture analysis confirmed the formation of bimodal (mixed grains) microstructural features in MPC + SPS specimens sintered at 350 °C, and 400 °C respectively due to the adhesion of fine grains (grain growth) and initiation of recrystallization at high temperatures. In addition to high density of twin structure, high-angle grain boundaries have also been identified. The power factor of 3.53 mW/m.K2 was obtained for the MPC + SPS at 400 °C due to increased Seebeck coefficient and larger electrical conductivity values. The maximum reduced thermal conductivity of 1.14W/mK was recorded due to a significant reduction in lattice thermal conductivity, which is mainly owing to strong scattering of phonons at the formation of mixed grain microstructures with high-density dislocations. As a result, maximum figure of merit, ZT = 1.17was achieved for MPC + SPS at 400 °C temperature.

Neutron-irradiated effect on the thermoelectric properties of Bi2Te3-based thermoelectric leg

Thermoelectric (TE) materials working in radioisotope thermoelectric generators are irradiated by neutrons throughout its service; thus, investigating the neutron irradiation stability of TE devices is necessary. Herein, the influence of neutron irradiation with fluences of 4.56 × 1010 and 1 × 1013 n/cm2 by pulsed neutron reactor on the electrical and thermal transport properties of n-type Bi2Te2.7Se0.3 and p-type Bi0.5Sb1.5Te3 thermoelectric alloys prepared by cold-pressing and molding is investigated. After neutron irradiation, the properties of thermoelectric materials fluctuate, which is related to the material type and irradiation fluence. Different from p-type thermoelectric materials, neutron irradiation has a positive effect on n-type Bi2Te2.7Se0.3 materials. This result might be due to the increase of carrier mobility and the optimization of electrical conductivity. Afterward, the effects of p-type and n-type TE devices with different treatments on the output performance of TE devices are further discussed. The positive and negative effects caused by irradiation can cancel each other to a certain extent. For TE devices paired with p-type Bi0.5Sb1.5Te3 and n-type Bi2Te2.7Se0.3 thermoelectric legs, the generated power and conversion efficiency are stable after neutron irradiation.

Thermal conductivity measurement of thermoelectric films using transient Photo-Electro-Thermal technique

Accurate and rapid measurement of thermal conductivity of thin films has been a challenge so far in the field of thermoelectric (TE) materials and devices. Herein, we proposed to use a transient photo-electro-thermal (TPET) technique to measure the thermal conductivity of TE thin-films with convenience. Combining theoretical and experimental methods, we found that the TPET technique using laser beam heating can significantly reduce the influence of Peltier effect and thus achieve high test accuracy. The measurement uncertainty of TPET technique for TE films can be depressed below 10%. Furthermore, this method is not only applicable for free-standing thin film, but also for thin film deposited on as-known substrates. Finally, thermal conductivity of several films including p-type Bi0.5Sb1.5Te3, n-type Ag2Se, and n-type Bi2Te3 deposited on PI film at different temperature are accurately measured, which demonstrates the wide applicability of TPET technique on semiconductor films.

Prominently optimized thermoelectric performance via possibly magnified carrier energy filtering effect in sandwich-structured p-type Cu-doped Bi0.5Sb1.5Te3 films

Prominently optimized thermoelectric performance via possibly magnified carrier energy filtering effect in sandwich-structured p-type Cu-doped Bi0.5Sb1.5Te3 films