skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Into the Void: Single Nanopore in Colloidally Synthesized Bi 2 Te 3 Nanoplates with Ultralow Lattice Thermal Conductivity
Bi2Te3 is a well-known thermoelectric material that was first investigated in the 1960s, optimized over decades, and is now one of the highest performing room-temperature thermoelectric materials to-date. Herein, we report on the colloidal synthesis, growth mechanism, and thermoelectric properties of Bi2Te3 nanoplates with a single nanopore in the center. Analysis of the reaction products during the colloidal synthesis reveals that the reaction progresses via a two-step nucleation and epitaxial growth: first of elemental Te nanorods and then the binary Bi2Te3 nanoplate growth. The rates of epitaxial growth can be controlled during the reaction, thus allowing the formation of a single nanopore in the center of the Bi2Te3 nanoplates. The size of the nanopore can be controlled by changing the pH of the reaction solution, where larger pores with diameter of similar to 50 nm are formed at higher pH and smaller pores with diameter of similar to 16 nm are formed at lower pH. We propose that the formation of the single nanopore is mediated by the Kirkendall effect and thus the reaction conditions allow for the selective control over pore size. Nanoplates have well-defined hexagonal facets as seen in the scanning and transmission electron microscopy images. The single nanopores have a thin amorphous layer at the edge, revealed by transmission electron microscopy. Thermoelectric properties of the pristine and single-nanopore Bi2Te3 nanoplates were measured in the parallel and perpendicular directions. These properties reveal strong anisotropy with a significant reduction to thermal conductivity and increased electrical resistivity in the perpendicular direction due to the higher number of nanoplate and nanopore interfaces. Furthermore, Bi2Te3 nanoplates with a single nanopore exhibit ultralow lattice thermal conductivity values, reaching similar to 0.21 Wm(-1)K(-1) in the perpendicular direction. The lattice thermal conductivity was found to be systematically lowered with pore size, allowing for the realization of a thermoelectric figure of merit, zT of 0.75 at 425 K for the largest pore size.  more » « less
Award ID(s):
2307231
PAR ID:
10589996
Author(s) / Creator(s):
; ; ; ; ; ;
Publisher / Repository:
American Chemical Society
Date Published:
Journal Name:
Chemistry of Materials
Volume:
36
Issue:
13
ISSN:
0897-4756
Page Range / eLocation ID:
6618 to 6626
Subject(s) / Keyword(s):
High-Thermoelectric Performance Bismuth Telluride 2D nanoplates
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. N/A (Ed.)
    Thermoelectrics are an important class of materials with great potential in alternative energy applications. In this study, two-dimensional (2D) nanoplates of the layered chalcogenides, Sb2Te3 and Bi2Te3, are synthesized and composites of the two are investigated for their thermoelectric properties. The two materials, Sb2Te3 and Bi2Te3, were synthesized as hexagonal, 2D nanoplates via a colloidal polyol route. The as-synthesized Sb2Te3 and Bi2Te3 vary drastically from one another in their lateral and vertical dimensions as revealed by scanning electron microscopy and atomic force microscopy. The single crystalline nanoplate nature is deduced by high-resolution transmission electron microscopy and selected area electron diffraction. Nanoplates have well-defined hexagonal facets as seen in the scanning and transmission electron microscopy images. The nanoplates were consolidated as an anisotropic nanostructured pellet via spark plasma sintering. Preferred orientation observed in the powder X-ray diffraction pattern and scanning electron microscopy images of the fractured pellets confirm the anisotropic structure of the nanoplates. Thermoelectric properties in the parallel and perpendicular directions were measured, revealing strong anisotropy with a significant reduction to thermal conductivity in the perpendicular direction due to increased phonon scattering at nanoplate interfaces. All compositions, except that of the 25% Bi2Te3 nanoplate composite, behave as degenerate semiconductors with increasing electrical resistivity as the temperature increases. The Seebeck coefficient is also increased dramatically in the nanocomposites, the highest reaching 210 μV/K for 15% Bi2Te3. The increase in Seebeck is attributed to energy carrier filtering at the nanoplate interfaces. Overall, these enhanced thermoelectric properties lead to a drastic increase in the thermoelectric performance in the perpendicular direction, with zT ∼ 1.26, for the 15% Bi2Te3 nanoplate composite at 450 K. 
    more » « less
  2. Controlling nanoporosity to favorably alter multiple properties in layered crystalline inorganic thin films is a challenge. Here, we demonstrate that the thermoelectric and mechanical properties of Ca 3 Co 4 O 9 films can be engineered through nanoporosity control by annealing multiple Ca(OH) 2 /Co 3 O 4 reactant bilayers with characteristic bilayer thicknesses (b t ). Our results show that doubling b t , e.g. , from 12 to 26 nm, more than triples the average pore size from ∼120 nm to ∼400 nm and increases the pore fraction from 3% to 17.1%. The higher porosity film exhibits not only a 50% higher electrical conductivity of σ ∼ 90 S cm −1 and a high Seebeck coefficient of α ∼ 135 μV K −1 , but also a thermal conductivity as low as κ ∼ 0.87 W m −1 K −1 . The nanoporous Ca 3 Co 4 O 9 films exhibit greater mechanical compliance and resilience to bending than the bulk. These results indicate that annealing reactant multilayers with controlled thicknesses is an attractive way to engineer nanoporosity and realize mechanically flexible oxide-based thermoelectric materials. 
    more » « less
  3. Abstract Stability, long lifetime, resilience against clogging, low noise, and low cost are five critical cornerstones of solid‐state nanopore technology. Here, a fabrication protocol is described wherein >1 million events are obtained from a single solid‐state nanopore with both DNA and protein at the highest available lowpass filter (LPF, 100 kHz) of the Axopatch 200B–the highest event count mentioned in literature. Moreover, a total of ≈8.1 million events are reported in this work encompassing the two analyte classes. With the 100 kHz LPF, the temporally attenuated population is negligible while with the more ubiquitous 10 kHz, ≈91% of the events are attenuated. With DNA experiments, the pores are operational for hours (typically >7 h) while the average pore growth is merely ≈0.16 ± 0.1 nm h −1 . The current noise is exceptionally stable with traces typically showing <10 pA h −1 increase in noise. Furthermore, a real‐time method to clean and revive pores clogged with analyte with the added benefit of minimal pore growth during cleaning (< 5% of the original diameter) is showcased. The enormity of the data collected herein presents a significant advancement to solid‐state pore performance and will be useful for future ventures such as machine learning where large amounts of pristine data are a prerequisite. 
    more » « less
  4. Abstract Nanoparticles embedded within a crystalline solid serve as impurity phonon scattering centers that reduce lattice thermal conductivity, a desirable result for thermoelectric applications. Most studies of thermal transport in nanoparticle-laden composite materials have assumed the nanoparticles to possess a single size. If there is a distribution of nanoparticle sizes, how is thermal conductivity affected? Moreover, is there a best nanoparticle size distribution to minimize thermal conductivity? In this work, we study the thermal conductivity of nanoparticle-laden composites through a molecular dynamics approach which naturally captures phonon scattering processes more rigorously than previously used analytical theories. From thermal transport simulations of a systematic variety of nanoparticle configurations, we empirically formulate how nanoparticle size distribution, particle number density, and volume fraction affect the lattice thermal conductivity. We find at volume fractions below 10%, the particle number density is by far the most impactful factor on thermal conductivity and at fractions above 10%, the effect of the size distribution and number density is minimal compared to the volume fraction. In fact, upon comparisons of configurations with the same particle number density and volume fractions, the lattice thermal conductivity of a single nanoparticle size can be lower than that of a size distribution which contradicts intuitions that a single size would attenuate phonon transport less than a spectrum of sizes. The random alloy, which can be considered as a single size configuration of maximum particle number density where the nanoparticle size is equal to the lattice constant, is the most performant in thermal conductivity reduction at volume fractions below 10%. We conclude that nanoparticle size distribution only plays a minor role in affecting lattice thermal conductivity with the particle number density and volume fraction being the more significant factors that should be considered in fabrication of nanoparticle-laden composites for potential improved thermoelectric performance. 
    more » « less
  5. The ferrimagnetic inverse spinel NiCo 2 O 4 has attracted extensive research interest for its versatile electrochemical properties, robust magnetic order, high conductivity, and fast spin dynamics, as well as its highly tunable nature due to the closely coupled charge, spin, orbital, lattice, and defect effects. Single-crystalline epitaxial thin films of NiCo 2 O 4 present a model system for elucidating the intrinsic physical properties and strong tunability, which are not viable in bulk single crystals. In this Perspective, we discuss the recent advances in epitaxial NiCo 2 O 4 thin films, focusing on understanding its unusual magnetic and transport properties in light of crystal structure and electronic structure. The perpendicular magnetic anisotropy in compressively strained NiCo 2 O 4 films is explained by considering the strong spin–lattice coupling, particularly on Co ions. The prominent effect of growth conditions reveals the complex interplay between the crystal structure, cation stoichiometry, valence state, and site occupancy. NiCo 2 O 4 thin films also exhibit various magnetotransport anomalies, including linear magnetoresistance and sign change in anomalous Hall effect, which illustrate the competing effects of band-intrinsic Berry phase and impurity scattering. The fundamental understanding of these phenomena will facilitate the functional design of NiCo 2 O 4 thin films for nanoscale spintronic applications. 
    more » « less