Substrate temperature-dependent thermoelectric figure of merit of nanocrystalline Bi2Te3 and Bi2Te2.7Se0.3 prepared using pulsed laser deposition supported by DFT study

This work reports the pulsed laser deposition of n-type selenium (Se) doped bismuth telluride (Bi₂Te_2.7Se_0.3) and n-type bismuth telluride (Bi₂Te₃) nanostructures under varying substrate temperatures. The influence of the substrate temperature during deposition on the structural, morphological and thermoelectric properties for each phase was investigated. Density functional theory (DFT) simulations were employed to study the electronic structures of the unit-cells of the compounds as well as their corresponding partial and total densities of states. Surface and structural characterization results revealed highly crystalline nanostructures with abundant grain boundaries. Systematic comparative analysis to determine the effect of Se inclusion into the Bi₂Te₃ matrix on the thermoelectric properties is highlighted. The dependence of the thermoelectric figure of merit (ZT) of the nanostructures on the substrate temperatures during deposition was demonstrated. The remarkable room temperature thermoelectric power factor (PF) of 2765 μW/mK² and 3179 μW/mK² for pure and Se-doped Bi₂Te₃ compounds respectively, signifies their potential of being useful in cooling and power generation purposes. The room temperature ZT values of the Se-doped Bi₂Te₃ was found to be 0.92, about 30% enhancement as compared with the pure phase, which evidently results from the suppressed thermal conductivity in the doped species caused by phonon scattering at the interfaces.     

Enhanced thermal stability of Bi2Te3-based alloys via interface engineering with atomic layer deposition

The ease of Te sublimation from Bi₂Te₃-based alloys significantly deteriorates thermoelectric and mechanical properties via the formation of voids. We propose a novel strategy based on atomic layer deposition (ALD) to improve the thermal stability of Bi₂Te₃-based alloys via the encapsulation of grains with a ZnO layer. Only a few cycles of ZnO ALD over the Bi₂Te_2.7Se_0.3 powders resulted in significant suppression of the generation of pores in Bi₂Te_2.7Se_0.3 extrudates and increased the density even after post-annealing at 500 °C. This is attributed to the suppression of Te sublimation from the extrudates. The ALD coating also enhanced grain refinement in Bi₂Te_2.7Se_0.3 extrudates. Consequently, their mechanical properties were significantly improved by the encapsulation approach. Furthermore, the ALD approach yields a substantial improvement in the figure-of-merit after the post-annealing. Therefore, we believe the proposed approach using ALD will be useful for enhancing the mechanical properties of Bi₂Te₃-based alloys without sacrificing thermoelectric performance.     

Boosting the thermoelectric performance of Bi2O2Se by isovalent doping

N‐type Bi₂O₂Se has a bright prospect for mid‐temperature thermoelectric applications on account of the intrinsically low thermal conductivity. However, the low carrier concentration of Bi₂O₂Se (~10¹⁵ cm^?3) severely limits its thermoelectric performance. Herein, the boosting of the carrier concentration to ~10¹⁹ cm^?3 can be realized in our La‐doped Bi₂O₂Se ceramic samples, which could be ascribed to the formation of isoelectronic traps and the narrowing of band gap, and contribute to a marked increase in the electrical conductivity (from 0.03 S cm^?1 to 182 S cm^?1). Our X‐ray absorption near‐edge structure spectra results reveal that a local disordering of oxygen atoms could be an important reason for the intrinsically low thermal conductivity of Bi₂O₂Se, and the point defects can also suppress the lattice thermal conductivity in La‐doped Bi₂O₂Se. The ZT value can be enhanced by a factor of ~4.5 to 0.35 at 823 K for Bi_1.98La_0.02O₂Se as compared to the pristine Bi₂O₂Se. The coordinated optimization of electrical and thermal properties demonstrates an effective method for the rational design of high‐performance thermoelectric materials.     

A thermoelectric generator comprising selenium-doped bismuth telluride on flexible carbon cloth with n-type thermoelectric properties

Carbon cloth was used as a flexible substrate for bismuth telluride (Bi₂Te₃) particles to provide flexibility and improve the overall thermoelectric performance. Bi₂Te₃ on carbon cloth (Bi₂Te₃/CC) was synthesized via a hydrothermal reaction with various reaction times. After over 12 h, the Bi₂Te₃ particles showed a clear hexagonal shape and were evenly adhered to the carbon cloth. Selenium (Se) atoms were doped into the Bi₂Te₃ structure to improve its thermoelectric performance. The electrical conductivity increased with increasing Se-dopant content until 40% Se was added. Moreover, the maximum power factor was 1300 μW/mK² at 473 K for the 30% Se-doped sample. The carbon cloth substrate maintained its electrical resistivity and flexibility after 2000 bending cycles. A flexible thermoelectric generator (TEG) fabricated using the five pairs of 30% Se-doped sample showed an open-circuit voltage of 17.4 mV and maximum power output of 850 nW at temperature difference ΔT = 30 K. This work offers a promising approach for providing flexibility and improving the thermoelectric performance of inorganic thermoelectric materials for wearable device applications using flexible carbon cloth substrate for low temperature range application.     

Synergistically optimizing electrical and thermal transport properties of Bi2O2Se ceramics by Te‐substitution

Bi₂O₂Se oxyselenides, characterized with intrinsically low lattice thermal conductivity and large Seebeck coefficient, are potential n‐type thermoelectric material in the mediate temperature range. Given the low carrier concentration of ~10¹⁵ cm^?3 at 300 K, the intrinsically low electrical conductivity actually hinders further enhancement of their thermoelectric performance. In this work, the isovalent Te‐substitution of Se plays an effective role in narrowing the band gap, which notably increases the carrier concentration to ~10¹⁸ cm^?3 at 300 K and the electron conduction activation energy has been lowered significantly from 0.33 to 0.14 eV. As a consequence, the power factor has been improved from 104 μW·K^?2·m^?1 for pristine Bi₂O₂Se to 297 μW·K^?2·m^?1 for Bi₂O₂Se_0.96Te_0.04 at 823 K. Meanwhile, the suppressed lattice thermal conductivity derives from the introduced point defects by heavier Te atoms. The gradually decreased phonon mean free path reflects the increasingly intense phonon scattering. Ultimately, the ZT value attains 0.28 for Bi₂O₂Se_0.96Te_0.04 at 823 K, an enhancement by a factor of ~2 as compared to that of pristine Bi₂O₂Se. This study has demonstrated that Te‐substitution of Se could synergistically optimize the electrical and thermal properties thus effectively enhancing the thermoelectric performance of Bi₂O₂Se.     

Enhancements of thermoelectric performance in n-type Bi2Te3-based nanocomposites through incorporating 2D Mxenes

Bi₂Te_2.7Se_0.3 compound has been considered as an efficient n-type room-temperature thermoelectric (TE) material. However, the large-scale applications for low-quality energy harvesting were limited due to its low energy-conversion efficiency. We demonstrate that TE performance of Bi₂Te_2.7Se_0.3 system is optimized by 2D Ti₃C₂T_x additive. Here, a 43% reduction of electrical resistivity is obtained for the nanocomposites at 380 K, originating from the increased carrier concentration. Consequently, the g = 0.1 sample shows a maximum power factor of 1.49 Wmm^?1K^?2. Meanwhile, the lattice thermal conductivity for nanocomposite samples is reduced from 0.77 to 0.41 Wm^?1K^?1 at 380 K, due to the enhanced phonon scattering induced by the interfaces between Ti₃C₂T_x nanosheets and Bi₂Te_2.7Se_0.3 matrix. Therefore, a peak ZT of 0.68 is achieved at 380 K for Bi₂Te_2.7Se_0.3/0.1 wt% Ti₃C₂T_x, which is enhanced by 48% compared with pristine sample. This work provides a new route for optimizing TE performance of Bi₂Te_2.7Se_0.3 materials.     

Electrochemically deposited thermoelectric n-type Bi2Te3 thin films

Electrochemically deposited n-type BiTe alloy thin films were grown from nitric acid baths on sputtered Bi_xTe_y/SiO/Si substrates. The film compositions, which varied from 57 to 63 at.% Te were strongly dependent on the deposition conditions. Surface morphologies varied from needle-like to granular structures depending on deposited Te content. Electrical and thermoelectric properties of these electrodeposited Bi_xTe_y thin films were measured before and after annealing and compared to those of bulk Bi₂Te₃. Annealing at 250 °C in reducing H₂ atmosphere enhanced thermoelectric properties by reducing film defects. In-plane electrical resistivity was highly dependent on composition and microstructure. In-plane Hall mobility decreased with increasing carrier concentration, while the magnitude of the Seebeck coefficient increased with increasing electrical conductivity to a maximum of −188.5 μV/K. Overall, the thermoelectric properties of electrodeposited n-type BiTe thin films after annealing were comparable to those of bulk BiTe films.     

Fabrication and electrical properties of Bi2-xSbxTe3 ternary nanopillars array films

Highly oriented Bi_2-xSb_xTe₃ (x?=?0, 0.7, 1.1, 1.5, 2) ternary nanocrystalline films were fabricated using vacuum thermal evaporation method. Microstructures and morphologies indicate that Bi_2-xSb_xTe₃ films have pure rhombohedral phase with well-ordered nanopillars array. Bi, Sb and Te atoms uniformly distributed throughtout films with no precipitation. Electrical conductivity of Bi_2-xSb_xTe₃ films transforms from n-type to p-type when x?>?1.1. Metal-insulator transition was observed due to the incorporation of Sb in Bi₂Te₃. Bi_2-xSb_xTe₃ film with x?=?1.5 exhibits optimized electrical properties with maximum electrical conductivity σ of 2.95?×?10⁵ S?m^?1 at T?=?300?K, which is approximately ten times higher than that of the undoped Bi₂Te₃ film, and three times higher than previous report for Bi_0.5Sb_1.5Te₃ films and bulk materials. The maximum power factor PF of Bi_0.5Sb_1.5Te₃ nanopillars array film is about 3.83?μW?cm^?1 K^?2 at T?=?475?K. Highly oriented (Bi,Sb)₂Te₃ nanocrystalline films with tuned electronic transport properties have potentials in thermoelectric devices.     

Preparation and thermoelectric properties of Bi2SexTe3−x bulk materials

Bi₂Te₃ and Bi₂Se₃ nanoplates were synthesized by a microwave-assisted wet chemical method, and Bi₂Se_xTe_3−x (x=1, 2, 3) bulk nanocomposites were then prepared by hot pressing the Bi₂Te₃ and Bi₂Se₃ nanoplates at 80 MPa and 723 K in vacuum. The phase composition and microstructures of the bulk samples were characterized by powder X-ray diffraction and field-emission scanning electron microscopy, respectively. The electrical conductivity of the Bi₂Se_xTe_3−x bulk nanocomposites increases with increasing Se content, and the Seebeck coefficient value is negative, showing n-type conduction. The absolute Seebeck coefficient value decreases with increasing Se content. A highest power factor, 24.5 µWcm⁻¹ K⁻², is achieved from the sample of x=1 at 369 K among the studied samples.     

Enhancement of thermoelectric performance of N-type Bi2Te3 based thin films via in situ annealing during magnetron sputtering

In this work, n-type Bi₂Te₃ based thin films were prepared in 300 °C via DC magnetron sputtering, and influences of sputtering power and annealing time on thermoelectric properties of films were investigated. The raise of sputtering power brings about the improvement of deposited rate and enhancement of grain size. Taking the consideration that the large-sized grains are to phonon scattering, we determine the medial power of 30 W as the basic technical parameters for the purpose of further optimizing performance through an in situ annealing process. Subsequently, thin-film treated by in situ annealing process acts out an obvious reduction in electrical conductivity attributed to the decrease in carrier concentration. Especially, the film annealed for 40 min shows an enhancement in the Seebeck coefficient and leads to a maximum power factor 0.82 m W m⁻¹ K⁻² at 543 K.     

Thermoelectric transport and magnetoresistance of electrochemical deposited Bi2Te3 films at micrometer thickness

Bismuth telluride (Bi₂Te₃) is so far the best thermoelectric material for applications near room temperature, and also exhibits large magnetoresistance. While the electrochemical deposition approach can achieve effective growth of the Bi₂Te₃ films at micrometer thickness, the magnetoresistance transportation behavior of the electrochemically deposited Bi₂Te₃ films is yet not clear. In this work, we demonstrate the thermoelectric and magnetoresistance behaviors of the micrometer thick Bi₂Te₃ films deposited via electrochemical deposition approach. The optimum thermoelectric power factor is observed in the Bi₂Te₃ sample with electrochemical deposition thickness of ~6 μm followed by rapid photon annealing treatment, reaching the magnitude of ~1 μWcm⁻¹K⁻² that is similar to the previous reports. In contrast to the single crystalline or vacuum deposited Bi₂Te₃ or Bi₂Se₃ films, the electronic transportations of the electrochemically deposited Bi₂Te₃ are more influenced by the carrier scatterings by the grain boundaries and lattice defect. As a result, their magnetoresistance (MR) shows a distinguished non-monotonic behavior when varying the magnetic field, while the magnitude of their MR exhibits a positive temperature dependence. These MR behaviors largely differ to the previously reported ones from the single crystalline or vacuum deposited Bi₂Te₃ or Bi₂Se₃, in which cases their MR monotonically increases with the magnetic field and exhibits negative temperature dependence. This work reveals the previously overlooked role of grain boundary that also regulates the transportation properties of bismuth chalcogenides in the presence of magnetic field.     

Enhanced thermoelectric performance of p-type sintered BiSbTe-based composites with AgSbTe2 addition

Bismuth telluride-based materials have been widely used in the field of thermoelectric cooling near room temperature. However, the material utilization and device conversion efficiency were limited by the low thermoelectric performance and poor mechanical properties of commercial zone-melting materials. With an aim to optimize the comprehensive properties, we prepared the composite samples of Bi_0.48Sb_1.52Te₃ (BST)-x wt% AgSbTe₂ (x = 0, 0.05, 0.1, 0.2) via the hot pressing method. It was found that the AgSbTe₂ addition can effectively increase the carrier concentration and improve the power factor to 46 μW cm^?1 K^?2 at 300 K. Due to the introduction of dislocations, stress and Te inhomogeneities, the lattice thermal conductivity of the composite was significantly reduced to 0.69 W m^?1 K^?1 at 325 K. As a result, a maximum ZT of 1.15 at 325 K is obtained for the x = 0.1 sample. Interestingly, BST-0.1 wt% AgSbTe₂ exhibits roughly isotropic thermoelectric performance perpendicular to and parallel to the pressing direction. Our study suggests that the BST-AgSbTe₂ composite is very promising for the application of thermoelectric refrigeration near room temperature.     

Electrophoretic co-deposition of Bi2O3–multiwalled carbon nanotubes coating as supercapacitor electrode

Nafion is suggested as an efficient assistant in preparing supercapacitor by employing nanoparticles. In this work, using a bi-additive of 0.10-mM NaOH + 0.10 g L⁻¹ Nafion, Nafion-assisted electrophoretic co-deposition of Bi₂O₃–multiwalled carbon nanotubes (MWCNTs) coating is successfully realized in ethanol solvent. The capacitance performances of the electrophoretic coatings in 6.0-M KOH electrolyte are investigated by cyclic voltammetry and galvanostatic charge–discharge techniques. Comparing with Bi₂O₃ coating prepared with electrophoretic deposition (EPD) by employing other additive (such as polyethyleneimine), the Bi₂O₃ coating prepared by Nafion-assisted EPD shows a better capacitance performance. Benefiting from the improvement in coating conductivity caused by MWCNTs, with a small additional amount of 4.0 wt.%, the Bi₂O₃–MWCNTs coating exhibits an amazing 164% increase of mass-specific capacitance (473 F g⁻¹ at the current density of 1.0 A g⁻¹) in comparison with pure Bi₂O₃ coating (179 F g⁻¹ at the current density of 1.0 A g⁻¹). The cyclic stability test exhibits excellent capacitance retention of 88.7% over 3000 cycles at a constant current density of 10.0 A g⁻¹. This work combines the advantages of MWCNTs, Nafion, and EPD to provide a facile route for preparing Bi₂O₃-based coating as a high-performance supercapacitor electrode.     

Enhancing the thermoelectric properties of super-lattice Al2O3/ZnO atomic film via interface confinement

Aluminum oxide (Al₂O₃)/zinc oxide (ZnO) thin films deposited via atomic layer deposition (ALD) are demonstrated to enhance their thermoelectric properties by manipulating them with a nano-thick Al₂O₃ interface. The overall superlattice structure is tuned by varying the ZnO ALD sequence and the Al₂O₃ ALD sequence while maintaining the same composition. An aluminum-doped zinc oxide (AZO) thin film is deposited at 250 °C, and the Al₂O₃ thickness in the superlattice is gradually increased from 0.13 nm to 1.23 nm. The total film composition is fixed at 2% AZO. We observe that an efficient superlattice structure is made with a specific Al₂O₃ thickness. The thermal conductivity is significantly decreased from 0.57 W/mK to 0.26 W/mK as the thickness of the Al₂O₃ layer is increased. Additionally, the absolute Seebeck coefficient is increased from 14 μV/K to 65 μV/K. This may be caused by the interface confinement effect and interface scattering between the ZnO layer and the Al₂O₃ layer. The figure of merit ZT value is 0.14 for the most efficient structure.     

A study on the thermoelectric properties of ALD-grown aluminum-doped tin oxide with respect to nanostructure modulations

The thermoelectric properties of aluminum-doped tin oxide (ATO) thin films synthesized by thermal atomic layer deposition (ALD) were studied with respect to the aluminum concentration. The overall aluminum content in each layer was modulated by adjusting the relative number of tin oxide (SnO₂) and aluminum oxide (Al₂O₃) growth cycles, where a sequential process involving n cycles of SnO₂ growth followed by 1 cycle of Al₂O₃ deposition was performed (building up a super-cycle). The electrical conductivity (620 S/cm), free carrier concentration (1.23x10²¹ cm^-3), and power factor (0.49 mW/K²m) increase until their maximum values are reached when the Al content is approximately 1.50 at% of the cations, and decrease as more Al is added in. On the other hand, the Seebeck coefficient decreases monotonically as the Al content increases up to about 2.88 at%, and begins to increase with further Al doping. Here the thermoelectric efficiency is therefore determined primarily by the free carrier concentration, while the Seebeck coefficient appears to be influenced by the overall crystal structure.     

Preparation and thermoelectric properties of MoS2/Bi2Te3 nanocomposites

MoS₂ nanosheets with size of several-hundred nanometers were prepared by a hydrothermal intercalation/exfoliation method, then MoS₂/Bi₂Te₃ composite nanopowders were prepared by a microwave-assisted wet chemical method using the MoS₂ nanosheets, TeO₂, Bi(NO₃)₃·5H₂O, KOH and ethylene glycol as raw materials. Bulk MoS₂/Bi₂Te₃ nanocomposites were prepared by hot pressing the MoS₂/Bi₂Te₃ composite nanopowders with MoS₂ nanosheet content ranging from 0 to 17 wt% at 80 MPa and 648 K in vacuum. X-ray photoelectron spectroscopy and X-ray diffraction analyses indicate that MoS₂ and Bi₂Te₃ did not react each other during the hot pressing. FESEM observation reveals that the MoS₂/Bi₂Te₃ composite samples had a more compact microstructure than the pristine Bi₂Te₃ bulk sample. The MoS₂ phase was relatively randomly dispersed in the composite. At a given temperature, the electrical conductivity of the composites increases first then decreases as the MoS₂ content increases, whereas the Seebeck coefficient of the bulk nanocomposites does not change much. A highest power factor, ~18.3 μW cm⁻¹ K⁻² which is about 30% higher than that of pristine Bi₂Te₃ sample, at 319 K has been achieved from a nanocomposite sample containing 6 wt% MoS₂.     

Enhanced Thermoelectric Properties of Bi2O2Se Ceramics by Bi Deficiencies

Polycrystalline Bi_2?xO₂Se ceramics were synthesized by spark plasma sintering process. Their thermoelectric properties were evaluated from 300 to 773 K. All the samples are layered structure with a tetragonal phase. The introduction of Bi deficiencies will cause the orientation alignment and change of effective mass. As a result, a significant enhancement of thermoelectric performance was achieved. The maximum of Seebeck coefficient is ?568.8 μV/K for Bi_1.9O₂Se at 773 K, much larger than ?445.6 μV/K for pristine Bi₂O₂Se. Featured with very low thermal conductivity [~0.6 W·(m·K)^?1] and an optimized electrical conductivity, ZT at 773 K is significantly increased from 0.05 for pristine Bi₂O₂Se to 0.12 for Bi_1.9O₂Se by introducing Bi deficiencies, which makes it a promising candidate for medium temperature thermoelectric applications.     

Chemical and electrochemical characterization of TiO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> atomic layer depositions on AZ-31 magnesium alloy

In this study, innovative TiO₂/Al₂O₃ mono/multilayers were applied by atomic layer depositions (ALD) on ASTM-AZ-31 magnesium/aluminum alloy to enhance its well-known scarce corrosion resistance. Four different configurations of ALD layers were tested: single TiO₂ layer, single Al₂O₃ layer, Al₂O₃/TiO₂ bilayer and Al₂O₃/TiO₂/Al₂O₃/TiO₂ multilayer deposited using Al[(CH₃)]₃ (trimethylaluminum, TMA), and TiCl₄ and H₂O precursors. All depositions were performed at 120°C to obtain an amorphous-like structure of both oxide layers. The four coatings were then investigated using different techniques, such as scanning electron microscope (SEM), stylus profilometer, glow discharge optical emission spectrometry (GDOES) and polarization curves in 0.05-M NaCl solution. The thickness of all the coatings was around 100 nm. The layers compositions were successfully investigated by the GDOES technique, although obtained data seem to be affected by substrate roughness and differences in sputtering rates between ceramic oxides and metallic magnesium alloy. Corrosion resistance showed to be strongly enhanced by the nanometric coatings, giving lower corrosion current densities in 0.05-M NaCl media with respect to the uncoated substrate (from 10⁻⁴ to 10⁻⁶ A/cm² for the single layers and from 10⁻⁴ to 10⁻⁸ A/cm² for the bi- and multilayers). All polarization curves on coated samples also showed a passive region, wider for the bi-layer (from −0.58 to −0.43 V with respect to Ag/AgCl) and multilayer (from −0.53 to −0.38 V with respect to Ag/AgCl) structures.     

The influence of CNTs on the thermoelectric properties of a CNT/Bi2Te3 composite

CNT/Bi₂Te₃ composites were prepared from composite powders in which CNTs were implanted in the Bi₂Te₃ matrix powders by a novel chemical route. It was found that the fabricated composite had a microstructure of a homogeneous dispersion of CNTs in the Bi₂Te₃ matrix due to interfacial bonding agents of oxygen atoms attaching to the surface of CNTs. The dimensionless figure of merit (ZT) of the composite shows significantly increased values compared to those of pure binary Bi₂Te₃ in the temperature range of 298–498 K and a maximum ZT of 0.85 was obtained at 473 K. It is considered that the improved thermoelectric performance of the composite mainly originated from thermal conductivity that was reduced by active phonon-scattering at the CNT/Bi₂Te₃ interface.     

High-throughput optimization and fabrication of Bi2Te2.7Se0.3-based artificially tilted multilayer thermoelectric devices

Artificially tilted multilayer thermoelectric devices (ATMTDs) have attracted growing attention due to their ease in miniaturization and high flexibility in device design. However, most of these devices are inefficient due to the lack of effective strategy to optimize their material matching and geometrical configurations. Herein, a high-throughput optimization approach is employed to screen high-performance Bi₂Te_2.7Se_0.3-based ATMTDs from a material genome database covering 230 kinds of candidates. 14 kinds of ATMTDs are found to have ZT_zx,max values exceeding 0.3 and tilt angles greater than 15°. Bi_0.1Sb_1.9Te₃/Bi₂Te_2.7Se_0.3 ATMTD is screened out and fabricated because of its excellent transverse figure of merit, large tilt angle, and good interface compatibility. Consequently, transverse figure of merit over 0.3, thermal sensitivity greater than 0.11 mV·K^?1, and power density up to 1.1 kW·m^?2 are recorded in Bi_0.1Sb_1.9Te₃/Bi₂Te_2.7Se_0.3 ATMTD. This indicates that ATMTDs have great potential for application in the fields of temperature detection and power generation.