High-Performance Flexible Bismuth Telluride Thin Film from Solution Processed Colloidal Nanoplates
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Binary pnictogen chalcogen compounds, primarily bismuth tellurides and selenides, are of great interest due to their applications in emerging quantum devices, as well as thermoelectric generators. The performance of bismuth telluride in these roles depends on its structure at the nanoscale, particularly the size, shape, and crystallinity of its nanocrystalline forms. However, current methods for controlling these features are often slow, inconsistent, or difficult to scale. Here, we demonstrate that through a solvothermal synthesis and hot injection process, precise control over the morphology of bismuth telluride nanoplates is possible with independent tuning of process variables, such as temperature and reaction time. We find that the nanoplate shape and internal porosity vary systematically with synthesis temperature and that the same morphological outcomes can be rapidly achieved at a fixed temperature by adjusting reaction duration. These results reveal that both the temperature and time can independently direct bismuth telluride morphological features, allowing for rapid, tunable synthesis strategies. Our approach offers a scalable framework, not only for bismuth telluride but also for related layered chalcogenides used in energy harvesting and quantum technologies.
The project succeeded in producing crack-free Bismuth Telluride thermoelectric parts with density exceeding 98% through laser powder bed fusion (LPBF) additive manufacturing (AM). This greatly exceeded the highest previously reported density of 88% and is the highest among all semiconducting materials processed by LPBF. The additively manufactured material shows comparable Seebeck coefficient as conventional form and can be made into complex geometries with reduced material loss. On the other hand, measured properties are dramatically sensitive to the AM process parameters used, such that with identical composition, the Seebeck coefficient can be controllably tuned from +120 µV/K to -207 µV/K, which means the material switches between an n-type to a p-type semiconductor depending on processing. These changes are accompanied by significant differences in the as-processed microstructure due to rapid solidification. A machine learning protocol was developed and greatly reduced the experimental burden of the project, reducing the typical process optimization period of 2 years to 6 months. The project was fully successful in the objective of producing defect-free, complex geometry of bismuth-telluride parts through LPBF, but only partially successful in achieving performance goals. First, cost reduction of manufacturing, as measured by material waste, was successfully reduced by up to 70% compared to conventional manufacturing methods. This exceeded the proposed 30% reduction in materials waste needed to reach the 20% cost reduction goal of the project. On the other hand, the device performance, as measured by Seebeck coefficient, failed to reach the 40% improvement in efficiency. Rather, we observe comparable Seebeck coefficient between AM samples and conventionally processed counterparts. The device-level efficiency improvement does exceed 40% for complex geometry samples due to shape-induced increase in temperature gradients, but this was not the originally proposed metric. The machine learning approach developed in this project greatly accelerated the process optimization and can be adopted for fast development of AM processing parameters for other brittle and otherwise difficult-to-print materials. For the public, we deliver an efficient and widely adoptable process for incorporating waste-heat harvesting thermoelectric devices in both industrial and commercial heat exchangers. The geometric flexibility allows the capturing device to conform to the shape of the heat source to improve the system-level conversion efficiency. The technique can be deployed on any commercial LBPF systems with zero modifications, thus poses minimal adoption barrier for any manufacturer that already employed AM technology. Beyond bismuth-telluride, the machine-learning guided optimization protocol can be used in the future to reduce both the time and cost of process development for AM of other energy conversion and harvesting materials.
The objective of this study is to evaluate the effect of ultrasonication on bismuth telluride nanocrystals prepared by solvothermal method. In this study, a low dimensional nanocrystal of bismuth telluride (Bi2Te3) was synthesized by a solvothermal process in an autoclave at 180 C and 200 psi. During the solvothermal reaction, organic surfactants effectively prevented unwanted aggregation of nanocrystals in a selected solvent while controlling the shape of the nanocrystal. The atomic ratio of bismuth and tellurium was determined by energy dispersive spectroscopy (EDS). The cavitational energy created by the ultrasonic probe was varied by the ultrasonication process time, while power amplitude remained constant. The nanocrystal size and its size distribution were measured by field emission scanning electron microscopy (FESEM) and a dynamic light scattering system. When the ultrasonication time increased, the average size of bismuth telluride nanocrystal gradually increased due to the direct collision of nanocrystals. The polydispersity of the nanocrystals showed a minimum when the ultrasonication was applied for 5 min. Keywords: bismuth telluride, nanocrystal, low-dimensional, ultrasonication, solvothermal
A new fabrication method for nanovoids-imbedded bismuth telluride (Bi--Te) material with low dimensional (quantum-dots, quantum-wires, or quantum-wells) structure was conceived during the development of advanced thermoelectric (TE) materials. Bismuth telluride is currently the best-known candidate material for solid-state TE cooling devices because it possesses the highest TE figure of merit at room temperature. The innovative process described here allows nanometer-scale voids to be incorporated in Bi--Te material. The final nanovoid structure such as void size, size distribution, void location, etc. can be also controlled under various process conditions.
We employed accumulative roll bonding to fabricate self‐standing metallurgical composite of in situ formed alkaline potassium‐bismuth‐telluride intermetallic K 2 (Bi 2/6 Te 3/6 Vac 1/6 ) embedded in potassium metal. This newly discovered thermodynamically stable potassiophilic crystal, termed “KBT”, is fcc antifluorite with K 2 Te archetype. Symmetric cells achieve 880 h of cycling at 0.5 mA cm −2 and 0.5 mAh cm −2 . Potassium metal battery (KMB) with Prussian blue (PB) cathode in carbonate electrolyte retains 80% capacity after 200 cycles at 1C. In ether‐based electrolyte with organic cathode, it achieves 80% retention after 900 cycles at 2C. Combined synchrotron X‐ray nano‐tomography, cryogenic‐focused ion beam microscopy (Cryo‐FIB) and sputter‐down X‐ray photoelectron spectroscopy (XPS) demonstrate uniform electrodeposits, versus baseline of potassium filaments intermixed with pores and coarse SEI. Binary K 3 Bi‐K and K 2 Te‐K intermetallic supports also provide improved electrochemical performance, albeit to lesser extent. Multiscale simulation provides insight into role of support structure in adatom energetics, film nucleation, early‐stage SEI morphology and interfacial stability.
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Thermoelectric generators have strong potential for aerospace and aircraft applications. However, traditional manufacturing methods for thermoelectric devices severely limit device adaptability and consequently marketability. Laser powder bed fusion is an additive manufacturing method which shows promising potential for producing thermoelectric devices. Thermoelectric materials pose unique challenges compared to metals because of low thermal conductivity, brittle fracture characteristics, and irregular powder particle morphologies. Herein, we communicate processing procedures to fabricate thermoelectric parts of Bi 2 Te 3 through laser powder bed fusion. In this study, we identify the successful combination of key process parameters—laser power, scan speed, hatch distance, and powder layer thickness—to achieve high-quality parts in terms of density and physical properties, and we demonstrate the impact of process parameter variation on built part quality. While it cannot exclusively determine part quality, the volumetric energy density is a useful guide in deciding process parameters for thermoelectric materials, and the optimal value is between 9 and 11 J/mm 3 for Bi 2 Te 3 . We demonstrate successful fabrication of different freeform geometries of Bi 2 Te 3 powders. The results suggest it is possible to extend this method more broadly to other semiconductor materials, including thermoelectric power generation materials applicable for space applications.
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We report on the thermal and thermoelectric properties of individual nanocrystalline Bi 2 Te 3 nanotubes synthesized by the solution phase method using 3ω method and a microfabricated testbench. Measurements show that the nanotubes offer improved ZT compared to bulk Bi 2 Te 3 near room temperature due to an enhanced Seebeck coefficient and suppressed thermal conductivity. This improvement in ZT originates from the nanocrystalline nature and low dimensionality of the nanotubes. Domain boundary filtering of low-energy electrons provides an enhanced Seebeck coefficient. The scattering of phonons at the surface of the nanotube leads to suppressed thermal conductivity. These have been theoretically analyzed using the Boltzmann equation based on the relaxation time approximation and Landauer approach. This work clearly demonstrates the possibility of achieving enhancement in thermoelectric efficiency by combining nanocrystalline and low-dimensional systems.
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Thermoelectric thin films exhibit different qualities when compared with bulk materials. The goal however is to achieve thermoelectric properties of bulk materials from electrodeposited thin films. Thin films are produced by electrochemical deposition at room temperature. In order to optimize thermoelectric figure of merit proper carrierconcentration must be obtained.
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