Sb2Te3 and Bi2Te3 Thin Films Grown by Room-Temperature MBE

Sb₂Te₃ and Bi₂Te₃ thin films were grown on SiO₂ and BaF₂ substrates at room temperature using molecular beam epitaxy. Metallic layers with thicknesses of 0.2?nm were alternately deposited at room temperature, and the films were subsequently annealed at 250°C for 2?h. x-Ray diffraction and energy-filtered transmission electron microscopy (TEM) combined with high-accuracy energy-dispersive x-ray spectrometry revealed stoichiometric films, grain sizes of less than 500?nm, and a texture. High-quality in-plane thermoelectric properties were obtained for Sb₂Te₃ films at room temperature, i.e., low charge carrier density (2.6?×?10¹⁹?cm^?3), large thermopower (130???V?K^?1), large charge carrier mobility (402?cm²?V^?1?s^?1), and resulting large power factor (29???W?cm^?1?K^?2). Bi₂Te₃ films also showed low charge carrier density (2.7?×?10¹⁹?cm^?3), moderate thermopower (?153???V?K^?1), but very low charge carrier mobility (80?cm²?V^?1?s^?1), yielding low power factor (8???W?cm^?1?K^?2). The low mobilities were attributed to Bi-rich grain boundary phases identified by analytical energy-filtered TEM.     

Effects of Reaction Temperature on Thermoelectric Properties of p-Type Nanostructured Bi2−x Sb x Te3 Prepared Using Hydrothermal Method and Evacuated-and-Encapsulated Sintering

We report fabrication of nanostructured Bi_2?x Sb _x Te₃ using hydrothermal method followed by cold-pressing and evacuated-and-encapsulated sintering techniques. To obtain lower resistivity, the reaction temperature in the hydrothermal synthesis is investigated, and the effects on the ZT values of Bi_2?x Sb _x Te₃ are reported. Both the x = 1.52 and 1.55 samples hydrothermally synthesized at 160°C show lower resistivity than the x = 1.55 sample hydrothermally synthesized at 140°C. However, the power factor is lower for the samples synthesized at 160°C due to the accompanying smaller thermopower. All three samples exhibit remarkably low thermal conductivity of around 0.41 W m^?1 K^?1 at room temperature. The peak ZT value occurs at 270 K for all three samples, being ZT = 1.75, 1.29, and 1.17 for x = 1.55 (synthesized at 140°C), 1.55 (synthesized at 160°C), and 1.52 (synthesized at 160°C), respectively.     

Nanostructure, Excitations, and Thermoelectric Properties of Bi2Te3-Based Nanomaterials

The effect of dimensionality and nanostructure on thermoelectric properties in Bi₂Te₃-based nanomaterials is summarized. Stoichiometric, single-crystalline Bi₂Te₃ nanowires were prepared by potential-pulsed electrochemical deposition in a nanostructured Al₂O₃ matrix, yielding transport in the basal plane. Polycrystalline, textured Sb₂Te₃ and Bi₂Te₃ thin films were grown at room temperature using molecular beam epitaxy and subsequently annealed at 250°C. Sb₂Te₃ films revealed low charge carrier density of 2.6?×?10¹⁹?cm^?3, large thermopower of 130???V?K^?1, and large charge carrier mobility of 402?cm²?V^?1?s^?1. Bi₂(Te_0.91Se_0.09)₃ and (Bi_0.26Sb_0.74)₂Te₃ nanostructured bulk samples were prepared from as-cast materials by ball milling and subsequent spark plasma sintering, yielding grain sizes of 50?nm and thermal diffusivities reduced by 60%. Structure, chemical composition, as well as electronic and phononic excitations were investigated by x-ray and electron diffraction, nuclear resonance scattering, and analytical energy-filtered transmission electron microscopy. Ab?initio calculations yielded point defect energies, excitation spectra, and band structure. Mechanisms limiting the thermoelectric figure of merit ZT for Bi₂Te₃ nanomaterials are discussed.     

Enhanced Thermoelectric Properties of Antimony Telluride Thin Films with Preferred Orientation Prepared by Sputtering a Fan-Shaped Binary Composite Target

p-Type antimony telluride (Sb₂Te₃) thermoelectric thin films were deposited on BK7 glass substrates by ion beam sputter deposition using a fan-shaped binary composite target. The deposition temperature was varied from 100°C to 300°C in increments of 50°C. The influence of the deposition temperature on the microstructure, surface morphology, and thermoelectric properties of the thin films was systematically investigated. x-Ray diffraction results show that various alloy composition phases of the Sb₂Te₃ materials are grown when the deposition temperature is lower than 200°C. Preferred c-axis orientation of the Sb₂Te₃ thin film became obvious when the deposition temperature was above 200°C, and thin film with single-phase Sb₂Te₃ was obtained when the deposition temperature was 250°C. Scanning electron microscopy reveals that the average grain size of the films increases with increasing deposition temperature and that the thin film deposited at 250°C shows rhombohedral shape corresponding to the original Sb₂Te₃ structure. The room-temperature Seebeck coefficient and electrical conductivity range from 101 μV K^?1 to 161 μV K^?1 and 0.81 × 10³ S cm^?1 to 3.91 × 10³ S cm^?1, respectively, as the deposition temperature is increased from 100°C to 300°C. An optimal power factor of 6.12 × 10^?3 W m^?1 K^?2 is obtained for deposition temperature of 250°C. The thermoelectric properties of Sb₂Te₃ thin films have been found to be strongly enhanced when prepared using the fan-shaped binary composite target method with an appropriate substrate temperature.     

High‐Performance Flexible Thermoelectric Devices Based on All‐Inorganic Hybrid Films for Harvesting Low‐Grade Heat

The fabrication of a flexible thermoelectric (TE) device that contains flexible, all‐inorganic hybrid thin films (p‐type single‐wall carbon nanotubes (SWCNTs)/Sb₂Te₃ and n‐type reduced graphene oxide (RGO)/Bi₂Te₃) is reported. The optimized power factors of the p‐type and n‐type hybrid thin films at ambient temperature are about 55 and 108 µW m^?1 K^?2, respectively. The high performance of these films that are fabricated through the combination of vacuum filtration and annealing can be attributed to their planar orientation and network structure. In addition, a TE device, with 10 couples of legs, shows an output power of 23.6 µW at a temperature gradient of 70 K. A prototype of an integrated photovoltaic‐TE (PV‐TE) device demonstrates the ability to harvest low‐grade “waste” thermal energy from the human body and solar irradiation. The flexible TE and PV‐TE device have great potential in wearable energy harvesting and management.     

Sequential Evaporation of Bi-Te Thin Films with Controllable Composition and Their Thermoelectric Transport Properties

We report a simplified sequential evaporation route that can deposit compositionally controllable Bi-Te thermoelectric (TE) thin films without the need for a highly controlled facility. Te and Bi granules were used as starting materials, with their ratio being adjusted to obtain Bi-Te films with different compositions and thicknesses. The as-evaporated and annealed films were subjected to structural and morphological analysis, and their transport properties were measured. X-Ray diffraction data revealed multiple phases for most films. Energy-dispersive x-ray spectroscopy showed that the film composition was Te-enriched due to the large vapor pressure difference of Te and Bi. A Bi₂Te₃ single phase was obtained in the annealed films, having nominal composition of BiTe_1.2. The existence of impurity phases, such as Bi₄Te₃ or elemental Te, was found in all the as-evaporated films and in the annealed films with other nominal Te/Bi ratios, which degraded the TE properties of the films by increasing their electrical conductivity and reducing their Seebeck coefficient. A pure Bi₂Te₃ film with nominal Te/Bi ratio of 1.2 exhibited a maximum power factor of 7.9 × 10^?4 W m^?1 K² after annealing at 200°C. This work demonstrated a simple, undemanding, reliable method to deposit Bi-Te-based TE thin films that can be utilized to fabricate low-cost TE microgenerators.     

Sputtered p-Type Sb2Te3/(Bi,Sb)2Te3 Soft Superlattices Created by Nanoalloying

In this work, p-type nanoscale ??soft superlattices?? consisting of multilayer stacks of 25?nm Sb₂Te₃ on 25?nm (Bi_0.2Sb_0.8)₂Te₃ were fabricated by nanoalloying. With this technique, nanoscale layers of the elements Bi, Sb, and Te are deposited by sputtering onto a Si/SiO₂ substrate and subsequently annealed to induce interdiffusion and a solid-state reaction to form the final superlattices. Different combinations of annealing temperatures were used in the annealing process. The in-plane electronic properties (Seebeck coefficient, electrical conductivity, charge carrier concentration, and carrier mobility) of these soft superlattices were examined. The cross-plane thermal conductivity was determined using time-domain thermal reflectance (TDTR). Secondary-ion mass spectrometry (SIMS) depth profiles reveal that the nanostructured thin films exhibit high stability against thermal interdiffusion during the annealing process. X-ray patterns of the samples display very strong texture with preferred c-orientation of the crystallites after the heat treatment. Scanning electron microscopy (SEM) cross-section images of the films show distinctly polycrystalline structure with increasing grain size for higher annealing temperatures, as confirmed by x-ray diffraction (XRD) analysis. Very high power factors exceeding 40???W/cm?K², similar to values for bulk single crystals with comparable compositions, are observed for the soft superlattices. The nanostructure appears to be stable up to 300°C. For a sample annealed at 150°C, a thermal conductivity as low as 0.45?W/mK was determined. Based on different assumptions concerning the degree of anisotropy of the transport properties, a cross-plane figure of merit ZT of 0.6 to 1.9 can be estimated for the thin films annealed at 300°C.     

Electrochemical Deposition and Characterization of Thermoelectric Ternary (Bi x Sb1?x )2Te3 and Bi2(Te1?y Se y )3 Thin Films

Thermoelectric thin films of the ternary compounds (Bi _x Sb_1?x )₂Te₃ and Bi₂(Te_1?y Se _y )₃ were synthesized using potentiostatic electrochemical deposition on gold-coated silicon substrates from aqueous acidic solutions at room temperature. The surface morphology, elemental composition, and crystal structure of the deposited films were studied and correlated with preparation conditions. The thermoelectric properties of (Bi _x Sb_1?x )₂Te₃ and Bi₂(Te_1?y Se _y )₃ films, i.e., Seebeck coefficient and electrical resistivity, were measured after transferring the films to a nonconductive epoxy support. (Bi _x Sb_1?x )₂Te₃ thin films showed p-type semiconductivity, and the highest power factor was obtained for film deposited at a relatively large negative potential with composition close to Bi_0.5Sb_1.5Te₃. In addition, Bi₂(Te_1?y Se _y )₃ thin films showed n-type semiconductivity, and the highest power factor was obtained for film deposited at a relatively small negative potential, having composition close to Bi₂Te_2.7Se_0.3. In contrast to Bi₂Te_2.7Se_0.3 thin films, an annealing treatment was required for Bi_0.5Sb_1.5Te₃ thin films to achieve the same magnitude of power factor as Bi₂Te_2.7Se_0.3. Therefore, Bi₂Te_2.7Se_0.3 thin films appear to be good candidates for multilayer preparation using electrochemical deposition, but the morphology of the films must be further improved.     

Fabrication of a Flexible Bismuth Telluride Power Generation Module Using Microporous Polyimide Films as Substrates

In this study, we investigated the effect of the structure of microporous p-type (Bi_0.4Te₃Sb_1.6) and n-type (Bi_2.0Te_2.7Se_0.3) BiTe-based thin films on their thermoelectric performance. High-aspect-ratio porous thin films with pore depth greater than 1 μm and pore diameter ranging from 300 nm to 500 nm were prepared by oxygen plasma etching of polyimide (PI) layers capped with a heat-resistant block copolymer, which acted as the template. The cross-plane thermal conductivities of the porous p- and n-type thin films were 0.4 W m^?1 K^?1 and 0.42 W m^?1 K^?1, respectively, and the dimensionless figures of merit, ZT, of the p- and n-type BiTe films were estimated as 1.0 and 1.0, respectively, at room temperature. A prototype thermoelectric module consisting of 20 pairs of p- and n-type strips over an area of 3 cm × 5 cm was fabricated on the porous PI substrate. This module produced an output power of 0.1 mW and an output voltage of 0.6 V for a temperature difference of 130°C. The output power of the submicrostructured module was 1.5 times greater than that of a module based on smooth BiTe-based thin films. Thus, the thermoelectric performance of the thin films was improved owing to their submicroscale structure.     

Improvement of Thermoelectric Properties in (Bi0.5Sb0.5)2Te3 Films of Nanolayered Pillar Arrays

In this work, it is found that unique pillar arrays with nanolayered structure can favorably influence the carrier and phonon transport properties of films. p-(Bi_0.5Sb_0.5)₂Te₃ pillar array film with (0 1 5) orientation was successfully achieved by a simple ion-beam-assisted technique at deposition temperature of 400°C, owing to the enhanced mobility of deposited atoms for more sufficient growth along the in-plane direction. The pillar diameter was about 250 nm, and the layered nanostructure was clear, with each layer in the pillar array being <30 nm. The properties of the oriented (Bi_0.5Sb_0.5)₂Te₃ pillar array were greatly enhanced in comparison with those of ordinary polycrystalline films synthesized at deposition temperature of 350°C and 250°C. The (Bi_0.5Sb_0.5)₂Te₃ pillar array film with (0 1 5) preferred orientation exhibited a thermoelectric dimensionless figure of merit of ZT = 1.25 at room temperature. The unique pillar array with nanolayered structure is the main reason for the observed improvement in the properties of the (Bi_0.5Sb_0.5)₂Te₃ film.     

Thin-Film Thermoelectric Modules for Power Generation Using Focused Solar Light

We demonstrated the fabrication of thin-film thermoelectric generators and evaluated their generation properties using solar light as a thermal source. Thin-film elements of Bi_0.5Sb_1.5Te₃ (p-type) and Bi₂Te_2.7Se_0.3 (n-type), which were patterned using the lift-off technique, were deposited on glass substrates using radiofrequency magnetron sputtering. After annealing at 300°C, the average Seebeck coefficients of p- and n-type films were 150???V/K and ?104???V/K, respectively, at 50°C to 75°C. A cylindrical lens was used to focus solar light to a line shape onto the hot side of the thin-film thermoelectric module with 15 p?Cn junctions. The minimum width of line-shaped solar light was 0.8?mm with solar concentration of 12.5 suns. We studied the properties of thermoelectric modules with different-sized p?Cn junctions on the hot side, and obtained maximum open voltage and power values of 140?mV and 0.7???W, respectively, for a module with 0.5-mm p?Cn junctions. The conversion efficiency was 8.75?×?10^?4%, which was approximately equal to the value estimated by the finite-element method.     

Electrodeposition of Sb x Te y Thermoelectric Films from Dimethyl Sulfoxide Solution

The electrochemical behaviors of nonaqueous dimethyl sulfoxide solutions containing Te^IV and Sb^III were investigated using cyclic voltammetry. On this basis, Sb _x Te _y thermoelectric films were prepared by the potentiodynamic electrodeposition technique from nonaqueous dimethyl sulfoxide solution, and the composition, morphology, and thermoelectric properties of the films were analyzed. Sb _x Te _y thermoelectric films prepared under different potential ranges all possessed smooth morphology. After annealing treatment at 200°C under N₂ protection for 4?h, all the deposited films showed p-type semiconductor properties. Sb_1.87Te_3.13 thermoelectric film, which most closely approached the stoichiometry of Sb₂Te₃ and possessed the highest Seebeck coefficient, could be potentiodynamically electrodeposited in the potential range of ?200?mV to ?600?mV.     

Enhancement of Thermoelectric Figure of Merit for Bi0.5Sb1.5Te3 by Metal Nanoparticle Decoration

Introducing nanoinclusions in thermoelectric (TE) materials is expected to lower the lattice thermal conductivity by intensifying the phonon scattering effect, thus enhancing their TE figure of merit ZT. We report a novel method of fabricating Bi_0.5Sb_1.5Te₃ nanocomposite with nanoscale metal particles by using metal acetate precursor, which is low cost and facile to scale up for mass production. Ag and Cu particles of ??40?nm were successfully near-monodispersed at grain boundaries of Bi_0.5Sb_1.5Te₃ matrix. The well-dispersed metal nanoparticles reduce the lattice thermal conductivity extensively, while enhancing the power factor. Consequently, ZT was enhanced by more than 25% near room temperature and by more than 300% at 520?K compared with a Bi_0.5Sb_1.5Te₃ reference sample. The peak ZT of 1.35 was achieved at 400?K for 0.1?wt.% Cu-decorated Bi_0.5Sb_1.5Te₃.     

Structure and Transport Properties of Bulk Nanothermoelectrics Based on Bi x Sb2−x Te3 Fabricated by SPS Method

Ball milling with subsequent spark plasma sintering (SPS) was used to fabricate bulk nanothermoelectrics based on Bi _x Sb_2?x Te₃. The SPS technique enables reduced size of grains in comparison with the hot-pressing method. The electrical and thermal conductivities, Seebeck coefficient, and thermoelectric figure of merit as functions of temperature and alloy composition were measured for different sintering temperatures. The greatest value of the figure of merit ZT = 1.25 was reached at the temperature of 90°C to 100°C in Bi_0.4Sb_1.6Te₃ for sintering temperature of 450°C to 500°C. The volume and quantitative distributions of size of coherent dispersion areas (CDA) were calculated for different sintering temperatures. The phonon thermal conductivity of nanostructured Bi _x Sb_2?x Te₃ was investigated theoretically taking into account phonon scattering on grain boundaries and nanoprecipitates.     

Fabrication of Highly (0?0?l)-Textured Sb2Te3 Film and Corresponding Thermoelectric Device with Enhanced Performance

An approach for fabrication of highly (0?0?l)-textured Sb₂Te₃ thin film with layered structure by the magnetron sputtering method is reported. The composition, microstructure, and thermoelectric properties of the thin films have been characterized and measured by x-ray diffraction, scanning electron microscopy with energy-dispersive x-ray spectroscopy, and a thermoelectric (TE) measurement system, respectively. The results show that well-oriented (0?0?l) Sb₂Te₃ thin film with layered structure is beneficial for improvement of thermoelectric properties, being a promising choice for planar TE devices. The power generation and cooling performance of a layered p-Sb₂Te₃ film device are superior to those of the ordinary thin-film device. For a typical parallel device with 38 layered Sb₂Te₃ film elements, the output voltage, maximum power, and corresponding power density are up to 10.3?mV, 11.1?μW, and 73?mW/cm², respectively, for a temperature difference of 76?K. The device can produce a 6.1?K maximum temperature difference at current of 45?mA. The results prove that enhanced microdevice performance can be realized by integrating (0?0?l)-oriented Sb₂Te₃ thin films with a layered architecture.     

The Effect of Annealing in Controlled Vapor Pressure on the Thermoelectric Properties of RF-Sputtered Bi2Te3 Film

To investigate the effect of annealing in controlled atmosphere on the thermoelectric properties of Bi-Te film, Te-deficient Bi-Te film was deposited by sputtering, and then annealed with various Bi-Te alloy powders with different Te concentrations in a closed system at 250°C for 24?h. Bi-Te phases other than Bi₂Te₃ in the as-deposited film could be removed when the film was annealed with Bi-Te source powder containing 62?at.% or higher content of Te. At the same time, the values of Seebeck coefficient and carrier concentration of the films approach ?105???V/K and 3?×?10¹⁹?cm^?3 to 6?×?10¹⁹?cm^?3, respectively. This result indicates that mass transport of Te to the film takes place, resulting in the formation of Bi₂Te₃ phase and reduction of the amount of p-type carriers due to compositional change of the film from Te-deficient to stoichiometric. Annealing in controlled Te-vapor atmosphere is an effective method to improve the thermoelectric properties of Bi-Te film by changing the composition and phase of Te-deficient film to stoichiometric Bi₂Te₃ film.     

In-situ monitoring of the growth of Bi2 Te2 and Sb2 Te3 films and Bi2 Te3-Sb2 Te3 superlattice using spectroscopic ellipsometry

In this work, we present in-situ monitoring of the growth of bismuth telluride (Bi₂Te₃) and antimony telluride (Sb₂Te₃) thin films as well as Bi₂ Te₃-Sb₂Te₃ superlattice using a spectroscopic ellipsometer (SE). Bi₂Te₃ and Sb₂ Te₃ films were grown by metalorganic chemical vapor deposition (MOCVD) at 350 C. A44-wavelength ellipsometer with spectral range from 404 nm to 740 nm was used in this work. The optical constants of Bi₂ Te₃ and Sb₂Te₃ at growth temperature were determined by fitting a model to the extracted in-situ SE data of optically thick Bi₂ Te₃ and Sb₂ Te₃ films. Compared to the optical constants of Bi₂ Te₃ and Sb₂ Te₃ at room temperature, significant temperature dependence was observed. Using their optical constants at growth temperature, the in-situ growth of Bi₂ Te₃ and Sb₂ Te₃ thin films were modeled and excellent fit between the experimental data and data generated from the best-fit model was obtained. In-situ growth of different Bi₂ Te₃-Sb₂ Te₃ superlattices was also monitored and modeled. The growth of Bi₂ Te₃ and Sb₂ Te₃ layers can be seen clearly in in-situ SE data. Modeling of in-situ superlattice growth shows perfect superlattice growth with an abrupt interface between the two constituent films.     

Thermopower Enhancement of Bi2Te3 Films by Doping I Ions

The thermoelectric properties of I-doped Bi₂Te₃ films grown by metal-organic chemical vapor deposition have been studied. I-doped epitaxial (00l) Bi₂Te₃ films were successfully grown on 4° tilted GaAs (001) substrates at 360 °C. I concentration in the Bi₂Te₃ films was easily controlled by the variation in a flow rate of H₂ carrier gas for the delivery of an isopropyliodide precursor. As I ions in the as-grown Bi₂Te₃ films were not fully activated, they did not influence the carrier concentration and thermoelectric properties. However, a post-annealing process at 400 °C activated I ions as a donor, accompanied with an increase in the carrier concentration. Interestingly, the I-doped Bi₂Te₃ films after the post-annealing process also exhibited enhancement of the Seebeck coefficient at the same electron concentration compared to un-doped Bi₂Te₃ films. Through doping I ions into Bi₂Te₃, the thermopower was also enhanced in Bi₂Te₃, and a high power factor of 5 × 10^?3 W K^?2 m^?1 was achieved.     

Low-Temperature,Solution-Based,Scalable Synthesis of Sb2Te3 Nanoparticles with an Enhanced Power Factor

Nanostructured thermoelectric (TE) materials, for example Sb₂Te₃, PbTe, and SiGe-based semiconductors, have excellent thermoelectric transport properties and are promising candidates for next-generation TE commercial application. However, it is a challenge to synthesize the corresponding pure nanocrystals with controlled size by low-temperature wet-chemical reaction. Herein, we report an alternative versatile solution-based method for synthesis of plate-like Sb₂Te₃ nanoparticles in a flask using SbCl₃ and Te powders as raw materials, EDTA-Na₂ as complexing agent, and NaBH₄ as reducing agent in the solvent (distilled water). To investigate their thermoelectric transport properties, the obtained powders were cold compacted into cuboid prisms then annealed under a protective N₂ atmosphere. The results showed that both the electrical conductivity (σ) and the power factor (S ² σ) can be enhanced by improving the purity of the products and by increasing the annealing temperature. The highest power factor was 2.04 μW cm^?1 K^?2 at 140°C and electrical conductivity remained in the range 5–10 × 10³ S m^?1. This work provides a simple and economic approach to preparation of large quantities of nanostructured Sb₂Te₃ with excellent TE performance, making it a fascinating candidate for commercialization of cooling devices.