skip to main content

Title: High-performance thermoelectric silver selenide thin films cation exchanged from a copper selenide template
Over the past decade, Ag 2 Se has attracted increasing attention due to its potentially excellent thermoelectric (TE) performance as an n-type semiconductor. It has been considered a promising alternative to Bi–Te alloys and other commonly used yet toxic and/or expensive TE materials. To optimize the TE performance of Ag 2 Se, recent research has focused on fabricating nanosized Ag 2 Se. However, synthesizing Ag 2 Se nanoparticles involves energy-intensive and time-consuming techniques with poor yield of final product. In this work, we report a low-cost, solution-processed approach that enables the formation of Ag 2 Se thin films from Cu 2−x Se template films via cation exchange at room temperature. Our simple two-step method involves fabricating Cu 2−x Se thin films by the thiol-amine dissolution of bulk Cu 2 Se, followed by soaking Cu 2−x Se films in AgNO 3 solution and annealing to form Ag 2 Se. We report an average power factor (PF) of 617 ± 82 μW m −1 K −2 and a corresponding ZT value of 0.35 at room temperature. We obtained a maximum PF of 825 μW m −1 K −2 and a ZT value of 0.46 at room temperature for our best-performing Ag 2 more » Se thin-film after soaking for 5 minutes. These high PFs have been achieved via full solution processing without hot-pressing. « less
; ; ; ; ; ; ; ;
Award ID(s):
1809112 1809064
Publication Date:
Journal Name:
Nanoscale Advances
Page Range or eLocation-ID:
368 to 376
Sponsoring Org:
National Science Foundation
More Like this
  1. There has been a growing interest in solution-phase routes to thermoelectric materials due to the decreased costs and novel device architectures that these methods enable. Many excellent thermoelectric materials are metal chalcogenide semiconductors and the ability to create soluble metal chalcogenide semiconductor precursors using thiol–amine solvent mixtures was recently demonstrated by others. In this paper, we report the first thermoelectric property measurements on metal chalcogenide thin films made in this manner. We create Cu 2−x Se y S 1−y and Ag-doped Cu 2−x Se y S 1−y thin films and study the interrelationship between their composition and room temperature thermoelectric properties. We find that the precursor annealing temperature affects the metal : chalcogen ratio, and leads to charge carrier concentration changes that affect the Seebeck coefficient and electrical conductivity. Increasing the Se : S ratio increases electrical conductivity and decreases the Seebeck coefficient. We also find that incorporating Ag into the Cu 2−x Se y S 1−y film leads to appreciable improvements in thermoelectric performance by increasing the Seebeck coefficient and decreasing thermal conductivity. Overall, we find that the room temperature thermoelectric properties of these solution-processed materials are comparable to measurements on Cu 2−x Se alloys made via conventional thermoelectric material processing methods. Achievingmore »parity between solution-phase processing and conventional processing is an important milestone and demonstrates the promise of this binary solvent approach as a solution-phase route to thermoelectric materials.« less
  2. Flexible thermoelectric generators (TEGs) have shown immense potential for serving as a power source for wearable electronics and the Internet of Things. A key challenge preventing large-scale application of TEGs lies in the lack of a high-throughput processing method, which can sinter thermoelectric (TE) materials rapidly while maintaining their high thermoelectric properties. Herein, we integrate high-throughput experimentation and Bayesian optimization (BO) to accelerate the discovery of the optimum sintering conditions of silver–selenide TE films using an ultrafast intense pulsed light (flash) sintering technique. Due to the nature of the high-dimensional optimization problem of flash sintering processes, a Gaussian process regression (GPR) machine learning model is established to rapidly recommend the optimum flash sintering variables based on Bayesian expected improvement. For the first time, an ultrahigh-power factor flexible TE film (a power factor of 2205 μW m −1 K −2 with a zT of 1.1 at 300 K) is demonstrated with a sintering time less than 1.0 second, which is several orders of magnitude shorter than that of conventional thermal sintering techniques. The films also show excellent flexibility with 92% retention of the power factor (PF) after 10 3 bending cycles with a 5 mm bending radius. In addition, a wearablemore »thermoelectric generator based on the flash-sintered films generates a very competitive power density of 0.5 mW cm −2 at a temperature difference of 10 K. This work not only shows the tremendous potential of high-performance and flexible silver–selenide TEGs but also demonstrates a machine learning-assisted flash sintering strategy that could be used for ultrafast, high-throughput and scalable processing of functional materials for a broad range of energy and electronic applications.« less
  3. In the past decade, great efforts have been devoted to the development of organic–inorganic hybrid perovskites for achieving efficient photovoltaics, but less attention has been paid to their thermoelectric applications. In this study, for the first time, we report the thermoelectric performance of 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) doped NH 2 CHNH 2 SnI 3 (FASnI 3 ) thin films. It is found that the electrical conductivities of the F4-TCNQ doped FASnI 3 thin films increase and then decrease along with increased doping levels of F4-TCNQ. Systematic studies indicate that enhanced electrical conductivities are attributed to the increased charge carrier concentrations and mobilities and superior film morphologies of the F4-TCNQ doped FASnI 3 thin films, and decreased electrical conductivities originate from the cracks and poor film morphology of the F4-TCNQ doped FASnI 3 thin films induced by excess F4-TCNQ dopants. The quantitative thermal conductivity scanning thermal microscopy studies reveal that the F4-TCNQ doped FASnI 3 thin films exhibit ultralow thermal conductivities. Moreover, the thermoelectric performance of the F4-TCNQ doped FASnI 3 thin films is investigated. It is found that the F4-TCNQ doped FASnI 3 thin films exhibit a Seebeck coefficient of ∼310 μV K −1 , a power factor of ∼130 μW mmore »−1 K −2 and a ZT value of ∼0.19 at room temperature. All these results demonstrate that our studies open a door for exploring cost-effective less-toxic organic–inorganic hybrid perovskites in heat-to-electricity conversion applications at room temperature.« less
  4. A solid‐state thermoelectric device is attractive for diverse technological areas such as cooling, power generation and waste heat recovery with unique advantages of quiet operation, zero hazardous emissions, and long lifetime. With the rapid growth of flexible electronics and miniature sensors, the low‐cost flexible thermoelectric energy harvester is highly desired as a potential power supply. Herein, a flexible thermoelectric copper selenide (Cu2Se) thin film, consisting of earth‐abundant elements, is reported. The thin film is fabricated by a low‐cost and scalable spin coating process using ink solution with a truly soluble precursor. The Cu2Se thin film exhibits a power factor of 0.62 mW/(m K2) at 684 K on rigid Al2O3substrate and 0.46 mW/(m K2) at 664 K on flexible polyimide substrate, which is much higher than the values obtained from other solution processed Cu2Se thin films (<0.1 mW/(m K2)) and among the highest values reported in all flexible thermoelectric films to date (≈0.5 mW/(m K2)). Additionally, the fabricated thin film shows great promise to be integrated with the flexible electronic devices, with negligible performance change after 1000 bending cycles. Together, the study demonstrates a low‐cost and scalable pathway to high‐performance flexible thin film thermoelectric devices from relatively earth‐abundant elements.

  5. Abstract

    Thermoelectric generators are an environmentally friendly and reliable solid‐state energy conversion technology. Flexible and low‐cost thermoelectric generators are especially suited to power flexible electronics and sensors using body heat or other ambient heat sources. Bismuth telluride (Bi2Te3) based thermoelectric materials exhibit their best performance near room temperature making them an ideal candidate to power wearable electronics and sensors using body heat. In this report, Bi2Te3thin films are deposited on a flexible polyimide substrate using low‐cost and scalable manufacturing methods. The synthesized Bi2Te3nanocrystals have a thickness of 35 ± 15 nm and a lateral dimension of 692 ± 186 nm. Thin films fabricated from these nanocrystals exhibit a peak power factor of 0.35 mW m−1·K−2at 433 K, which is among the highest reported values for flexible thermoelectric films. In order to evaluate the flexibility of the thin films, static and dynamic bending tests are performed while monitoring the change in electrical resistivity. After 1000 bending cycles over a 50 mm radius of curvature, the change in electrical resistance of the film is 23%. Using Bi2Te3solutions, the ability to print thermoelectric thin films with an aerosol jet printer is demonstrated, highlighting the potential of additive manufacturing techniques for fabricating flexible thermoelectric generators.