Bi Nanowires Research Articles

Insights into One-Dimensional Thermoelectric Materials: A Concise Review of Nanowires and Nanotubes.

This brief review covers the thermoelectric properties of one-dimensional materials, such as nanowires and nanotubes. The highly localised peaks of the electronic density of states near the Fermi levels of these nanostructured materials improve the Seebeck coefficient. Moreover, quantum confinement leads to discrete energy levels and a modified density of states, potentially enhancing electrical conductivity. These electronic effects, coupled with the dominance of Umklapp phonon scattering, which reduces thermal conductivity in one-dimensional materials, can achieve unprecedented thermoelectric efficiency not seen in two-dimensional or bulk materials. Notable advancements include carbon and silicon nanotubes and Bi3Te2, Bi, ZnO, SiC, and Si1-xGex nanowires with significantly reduced thermal conductivity and increased ZT. In all these nanowires and nanotubes, efficiency is explored as a function of the diameter. Among these nanomaterials, carbon nanotubes offer mechanical flexibility and improved thermoelectric performance. Although carbon nanotubes theoretically have high thermal conductivity, the improvement of their Seebeck coefficient due to their low-dimensional structure can compensate for it. Regarding flexibility, economic criteria, ease of fabrication, and weight, carbon nanotubes could be a promising candidate for thermoelectric power generation.

Lattice-dislocated bismuth nanowires formed by in-situ chemical etching on copper foam for enhanced electrocatalytic CO2 reduction

Electrochemical CO2 reduction reaction (CO2RR) to HCOOH is one of the most feasible and economical methods to achieve carbon neutrality. Bismuth (Bi), as a metal catalyst for CO2RR, is considered to have great potential for application and has been widely studied due to its high formate selectivity, low toxicity, cheapness, and abundance. Unfortunately, low current density and short electrode lifetime have hindered its progress towards practical applications. In this work, we present a method that enables the chemical etching of Bi on Cu, which is capable of spontaneously accomplishing the loading of Bi on Cu foam in the liquid phase at room temperature. Additionally, to provide more abundant catalytically active sites, twisted Bi nanowires (BiNWs) with lattice dislocations were successfully prepared on the surface of Cu foam using a three-step chemical method involving oxidation, reduction, and in-situ etching. The Cu Foam@BiNWs was found to be a highly active electrocatalyst for CO2 reduction to formate at a low applied potential, achieving a faradaic efficiency for formate (FEFormate) of 95 % and a formate partial current density of ∼ 12 mA cm−2 at −0.78 V vs. RHE (reversible hydrogen electrode). Even within such a wide potential window of −0.68 ∼ -1.08 V vs. RHE, the FEFormate is consistently above 90 %. Such exceptional CO2 reduction activity can be attributed to the distortions and lattice dislocations present in the surface BiNWs. Furthermore, the Cu Foam@BiNWs electrode demonstrated a total current density close to 100 mA cm−2 at −0.98 V in an alkaline flow cell, while maintaining excellent catalytic stability over a prolonged 30-hour period of high current density electrochemical activity, thus showing potential for advancing the industrialisation of formate production. This work emphasizes the crucial role of size-dependent catalysis and crystal defect engineering strategies in the field of electrocatalysis, elucidates the mechanism of the rate-determining step (RDS) in the electrocatalytic CO2 reduction process on the developed catalysts, which can provide valuable insights into the design and development of high performance electrocatalysts not only in CO2RR but also in other fields.

Growth mechanism of bismuth-filled nanoporous silicon with improved structural stability and low thermal conductivity

Nano porous silicon (PS) is a strong candidate for thermoelectric application, but it shows low structural stability and is prone to collapse. To enhance the structural stability of PS and offer a new way to improve its electrical conductivity, PS was prepared by electrochemical etching and Bi nanowires were fabricated in the pores of PS by electrodeposition. In addition, for studying the effect of structures on the properties of Bi-filled PS composites, aperiodic single-layer (SL) structure, and periodic rugate (Rgt) structure and Bragg structure PS samples were prepared by changing the etching current waveform and etching time. The results show that the initial Bi deposition position and filling fraction of Bi nanowires in PS templates can be precisely controlled. Since Bi nanowires have significantly different continuity in Rgt and Bragg structures compared with SL structures, we proposed two growth mechanisms of Bi nanowires, including the axis-growth mechanism and transverse-axis-growth mechanism, with the supports of the experimental results of XRD, SEM, and EDS.The room temperature thermal conductivities of pristine and Bi-filled PS layers are in the ranges of 4.5 ∼ 5.0 and 4.2 ∼ 6.0 W･m−1K−1, respectively, about 1/10 of the original unetched silicon wafer. No apparent increase of thermal conductivity was observed in any Bi-filled composites. In addition, the thermal conductivities of PS layers with Bragg structure, including pristine and Bi-filled PS composites, are significantly lower than those of the other two structures.SEM images also demonstrates that Bi greatly improved the mechanical property of PS composites, especially the periodic structures composites. This study firmly demonstrates that Bi-filling in PS with periodic Bragg structure is practical to obtain nanocomposites with low thermal conductivity and improved structural stability. It offers a new dimension to optimize the property of PS for thermoelectric application by pore configuration design and controllable nanowire Bi filling.

Influence of High Surfactant Concentrations on the Morphology and Crystallinity of Electrodeposited Antimony and Bismuth Nanowires

Antimony and bismuth nanowires are excellent model systems to investigate the interplay of various size-dependent transport phenomena relevant for applications in thermoelectrics, spintronics, or catalysis. The properties of these nanowires can be significant influenced by size effects due to the large mean free path and Fermi wavelength of charge carriers and phonons. Since antimony and bismuth possess highly anisotropic Fermi surfaces, the transport is also strongly dependent on the crystallographic orientation. Therefore, it is very important to develop and control suitable electrodeposition processes that allow us to understand the nanowire growth and to accordingly adjust preferred orientation and morphology of the synthesized nanowires.The so called template route employed in the presented work allows to control number density, alignment, geometry, length and diameter of the nanowires. The electrolytes and plating processes influence crystallinity, crystal orientation, and morphology of the electrodeposited materials. Here, antimony and bismuth nanowires are grown by potentiostatic electrodeposition in polycarbonate etched ion-track membranes using SbCl3 and BiCl3 in aqueous electrolytes.In this talk, we will show the influence of the presence of nonionic and anionic surfactants in high concentrations in the electrolyte during the electrodeposition of Bi and Sb nanowires. The recorded current-time curves of the plating process will be presented. Systematic characterization of the nanowires by scanning- and transmission electron microscopy, and X-ray diffraction reveal a strong change in crystallinity as a function of surfactant concentration, which will be discussed in detail.

Experimental evidence of a size-dependent sign change of the Seebeck coefficient of Bi nanowire arrays

The electrical transport in bismuth nanowires is strongly influenced by both sample geometry and crystallinity. Compared to bulk bismuth, the electrical transport in nanowires is dominated by size effects and influenced by surface states, which gain increasing relevance with increasing surface-to-volume ratios, i.e. with decreasing wire diameter. Bismuth nanowires with tailored diameter and crystallinity constitute, therefore, excellent model systems, allowing to study the interplay of the different transport phenomena. Here, we present temperature-dependent Seebeck coefficient and relative electrical resistance measurements of parallel bismuth nanowire arrays with diameters between 40 and 400 nm synthesized by pulsed electroplating in polymer templates. Both electrical resistance and Seebeck coefficient exhibit a non-monotonic temperature dependence, with the sign of the Seebeck coefficient changing from negative to positive with decreasing temperature. The observed behavior is size-dependent and is attributed to limitations of the mean free path of the charge carriers within the nanowires. The observed size-dependent Seebeck coefficient and in particular the size-dependent sign change opens a promising avenue for single-material thermocouples with p- and n-legs made from nanowires with different diameters.

Van der Waals Epitaxy of Bi Nanowires and Bi2Se3 Thin Films on an Antiferromagnetic Substrate of CoNb3S6

The combination of a topological insulator and an antiferromagnet is expected to exhibit the quantum anomalous Hall effect due to the breaking of the time-reversal symmetry. As a layered antiferromagnet, CoNb3S6 was recently found to exhibit an anomalous Hall effect below the Néel temperature (TN = 29 K). Here, we report the controllable growth of Bi nanowires and Bi2Se3 thin films on CoNb3S6 substrates using molecular beam epitaxy. The composition and morphology of the as-prepared Bi nanowires and Bi2Se3 thin films were studied by atomic force microscopy, X-ray photoelectron spectroscopy, and scanning tunneling microscopy. We found that the as-grown Bi nanowires with abundant sizes are oriented along high-symmetry directions of the substrate, forming firework-like structures. Such firework-like structures of Bi nanowires exhibit a high edge-to-surface ratio as well as a strong anisotropy, highly desirable for photoelectric devices and industrial catalysts. The absence of oxidation peaks verifies that the as-prepared samples are of high quality and air stability, very promising for applications.

Polycrystalline bismuth nanowire networks for flexible longitudinal and transverse thermoelectrics.

This paper reports on the preparation and the characterization of structural, electrical and thermoelectric properties of nanocomposite films formed from three-dimensional networks of polycrystalline bismuth (Bi) nanowires (NWs). The samples were fabricated by electrodeposition within polycarbonate (PC) templates with crossed cylindrical nanopores, yielding self-supported networks of Bi crossed nanowires (CNWs) with mean diameter values ranging from 23 nm to 230 nm. Temperature changes in electrical resistance and thermopower were studied by considering electric and thermal currents flowing in the plane of the films. While the values of the Seebeck coefficient are close to those of polycrystalline Bi for diameters greater than 100 nm, a progressive decrease in thermopower appears at smaller diameters, due to an increasing contribution of surface charge carriers as the diameter decreases. Transverse thermoelectricity based on the Nernst effect was also demonstrated on a network of Bi CNWs 230 nm in diameter. Such hierarchical architectures based on Bi CNWs are extremely robust, offering a reliable solution for the next generation of flexible thermoelectric devices.

Observing variations in carrier-scattering mechanisms of polycrystalline bismuth through its temperature-dependent properties

This study has investigated variations in the carrier scattering mechanisms of polycrystalline bismuth based on the temperature dependence of its transport coefficients across a range of temperatures from 10 to 300 K. A measurement of the continuous temperature dependence of the Hall coefficient revealed the characteristic extremes of its temperature-based parameters to be less than 50 K. The results demonstrated a clear variation in the component of the scattering mechanism pertaining to acoustic deformation. Furthermore, the temperature dependencies of carrier density, mobility, chemical potential, and band gap energy were also comprehensively investigated to determine their influence on carrier transport. The information obtained in this study is quite relevant for the realization of the carrier transport of Bi nanowire. The carrier transport of the wire exhibits a mean free path that is equivalent to the wire diameter and has been expected to introduce a quantum effect, thus enhancing the thermoelectric performance.

Effects of Size Reduction on the Electrical Transport Properties of 3D Bi Nanowire Networks

Abstract3D nanowire networks are fascinating systems for future microelectronic devices. They can be handled like macroscopic objects, while exhibiting properties of nanoscale materials. Here, the fabrication of free‐standing 3D bismuth nanowire networks with well‐controlled and systematically adjusted wire diameter and interconnectivity is presented. The samples are fabricated by pulse electroplating of bismuth into the pores of ion track‐etched membranes using an aqueous electrolyte. By optimizing the growth parameters, homogeneously grown, mechanically self‐supporting and free‐standing networks without a supporting matrix are achieved. Cross‐plane Seebeck coefficient and electrical resistance values are investigated as a function of nanowire diameter and temperature. The unique characteristics of these highly interconnected and mechanically self‐supported Bi 3D nanowire networks offer exciting perspectives for their implementation in, e.g., infrared detection based on thermoelectric effects, sensing, and THz applications.

Detection of hydrogen peroxide involving bismuth nanowires via template-free electrochemical synthesis using deep eutectic solvents

Nanomaterials with different morphologies have been important in the development of electrochemical sensors with applications in the biomedical field. In the last decade, there has been increasing interest in Bi-based nanostructures for sensing applications where green strategies are preferred. The template-free synthesis of Bi nanowires (BiNWs) involving deep eutectic solvents (DESs) as electrolytes has enabled the fabrication of a sensing platform with electrocatalytic activity towards hydrogen peroxide. The target molecule plays an important part in the development of cancers and its detection could shed light on the dynamics related to cellular metabolism, with applications in medical research. The BiNW-based platform is shown to detect the molecule of interest in the presence of common interfering agents and offers avenues for further development.

Beyond Volume Variation: Anisotropic and Protrusive Lithiation in Bismuth Nanowire.

Materials storing energy via an alloying reaction are promising anode candidates in rechargeable lithium-ion batteries (LIBs) due to their much higher energy density than the current graphite anode. Until now, the volumetric expansion of such electrode particles during lithiation has been considered as solely responsible for cycling-induced structural failure. In this work, we report different structural failure mechanisms using single-crystalline bismuth nanowires as the alloying-based anode. The Li-Bi alloying process exhibits a two-step transition, that is, Bi-Li1Bi and Li1Bi-Li3Bi. Interestingly, the Bi-Li1Bi phase transition occurs not only in the bulk Bi nanowire but also on the particle surface showing its characteristic behavior. The bulk alloying kinetics favors a Bi-(012)-facilitated anisotropic lithiation, whose mechanism and energetics are further studied using the density functional theory calculations. More importantly, the protrusion of Li1Bi nanograins as a result of anisotropic Li-Bi alloying is found to dominate the surface morphology of Bi particles. The growth kinetics of Li1Bi protrusions is understood atomically with the identification of two different controlling mechanisms, that is, the dislocation-assisted strain relaxation at the Bi/Li1Bi interface and the short-range migration of Bi supporting the off-Bi growth of Li1Bi. As loosely rooted to the bulk substrate and easily peeled off and detached into the electrolyte, these nanoscale protrusions developed during battery cycling are believed to be an important factor responsible for the capacity decay of such alloying-based anodes at the electrode level.

Cavity containing core-shell Bi@C nanowires toward high performance lithium ion batteries

Abstract Lithium ion batteries (LIBs) with high energy density are highly required. Bi is considered to be a promising anode candidate for lithium ion batteries (LIBs) due to its high volumetric and moderate gravimetric energy density, combined with peaceable operation voltage. However, the low conductivity and large volume change during repeated cycles greatly hinder the practical application of Bi-based anode materials in LIBs. Herein, we developed a very simple approach to synthesize Bi@C nanowires for lithium ion batteries, which are derived from controlled thermal reduction of (BiO)2CO3@polysaccharose (CRP) under reducing atmosphere. Carbonization of CRP combining with reduction of (BiO)2CO3 to metallic Bi result in formation of cavity containing Bi@C nanowires with non-adherent thin carbon layer confining metallic Bi nanowires. The unique cavity containing core-shell structure is beneficial for promoting the microscopic electrochemical reaction kinetics and maintaining structure stability of the electrode during cycling. Thus, the Bi@C anode exhibits good lithium storage and long-life cyclic performance, featured for a high capacity of 233 mA h g−1 at 100 mA g−1 after 350 cycles.

High-pressure, high temperature synthesis of a mesoporous α-quartz/bismuth nanowire composite

High temperature, high pressure conditions were used to insert liquid bismuth in 4–6 nm diameter amorphous silica nanotubes. A combination of transmission electron microscopy and neutron powder diffraction indicate that the final composite consists in 5–6 nm semi-conducting Bi nanowires confined in insulating mesoporous α-quartz. Such a nanostructured material could be of considerable interest for thermoelectric applications.

Evolution of Bi Nanowires from BiOBr Nanoplates Through a NaBH4 Reduction Method with Enhanced Photodegradation Performance

In this work, we have adopted a coprecipitation method to synthesize BiOBr nanoplates with diameter of 150–450 nm and thickness of 40–80 nm, and then created Bi nanowires (diameter: 6 nm) on their surface through a NaBH4 reduction method. Evolution of Bi nanowires was systematically investigated by varying the concentration of NaBH4 solution and reaction time. It is demonstrated that with increasing the NaBH4 concentration (2 h reaction), Bi nanowires are gradually evolved from BiOBr crystals, and in particular treatment by 110 mM NaBH4 solution leads to the complete evolution of BiOBr nanoplates to Bi nanowires. At a low-concentration NaBH4 solution (30 mM), BiOBr crystals are partially reduced to Bi nanowires with increasing reaction time, and then the Bi nanowires are recrystallized into BiOBr nanowires/nanoparticles on the surface of BiOBr nanoplates. At a high-concentration NaBH4 solution (110 mM), BiOBr nanoplates are easily reduced to Bi nanowires with a short reaction time, and further prolonging the reaction time leads to the gradual transformation of Bi nanowires into Bi4O5Br2 nanoparticles/nanowires. Photocatalytic performances of the samples were evaluated by eliminating rhodamine B from aqueous solution under simulated sunlight illumination. It is demonstrated that the creation of Bi nanowires (an appropriate content) on the surface of BiOBr nanoplates can produce excellent Bi@BiOBr composite photocatalysts with enhanced photodegradation performances. The underlying enhanced photocatalytic mechanism was investigated and discussed.

Bismuth nanowires: electrochemical fabrication, structural features, and transport properties

Electrochemical aspects of Bi electrocrystallization from a bath containing bismuth nitrate in a mixture of ethylene glycol and water are addressed. Bismuth nanowires with diameters of 50-120 nm and a length of up to a few dozen microns were prepared by electrodeposition into the pores of anodic aluminium oxide templates. Crystal structure and morphology of electrodeposited materials were characterized using electron microscopy, selected area electron diffraction, and X-ray diffraction analysis. Factors affecting the formation of single or polycrystalline nanowires and their crystallographic orientation are discussed. The prospects of electrodeposited Bi nanostructures for microelectronics are illustrated by the quantitative resistivity measurements of highly texturized Bi nanowires with a diameter of ca. 100 nm and a length varying from 160 to 990 nm in a temperature range from 300 to 1.2 K.

Bi nanowires modified by 400 keV and 1 MeV Au ions

We report on the modification of the structure and morphology of Bi nanowires of two different diameters (80 or 130 nm) exposed to beams of 400 keV and 1 MeV Au+ until complete wire degradation. For fluences up to ∼1 ion/nm2, the main effect was a slight roughening of the originally smooth surface and the appearance of a damaged zone at the wire edges. After an exposure to ∼2 ions/nm2, shallow (∼5-7 nm deep) but wide (up to 120nm) depressions are seen, giving the wires a “wavy” morphology. At the largest fluence tested (10 ions/nm2), the thickest nanowires present an amorphized structure containing an embedded dispersion of small spherical metallic crystallites, while the thinner wires collapse into large (∼50nm) nanoparticles composed of a crystalline core surrounded by a disordered oxidized shell. The observed morphologic modifications are discussed considering sputtering and radiation induced surface diffusion effects.

Wet-Chemical Synthesis of Enhanced-Thermopower Bi1−xSbx Nanowire Composites for Solid-State Active Cooling of Electronics

In 1993, Hicks and Dresselhaus [Thermoelectric figure of merit of a one-dimensional conductor, Phys. Rev. B 47, 16631 (1993).] suggested that Bi nanowires could result in values of the thermoelectric figure of merit zT > 1. The Dresselhaus group also calculated a ternary phase diagram for Bi1-xSbx nanowires as a function of x and wire diameter. This manuscript reports a wet-chemical method to synthesize Bi1-xSbx-silica nanowire composites. Resistivity, Hall electron concentration, electron mobility, Seebeck and Nernst coefficients, and thermal conductivity of composites are measured and compared to bulk polycrystalline Bi1-xSbx samples prepared either by ingot casting or by the same wet chemistry but without nanostructuring. A clear increase of the thermopower in 20-nm Bi94Sb6-silica is reported when compared to bulk samples, and the values are among the highest found in the literature from 300 to 380 K, even though the electron concentration is higher than in the bulk. This suggests that consistent with theory, size quantization is responsible for the thermopower increase.

Manifestations of Surface States in the Longitudinal Magnetoresistance of an Array of Bi Nanowires

The longitudinal magnetoresistance of the array of parallel-oriented bismuth nanowires each 100 nm in diameter grown by electrochemical deposition in nanopores of an Al2O3 membrane has been studied in magnetic fields up to 14 T and at temperatures down to 0.3 K. The resistance increases with the field and reaches a broad maximum in fields about 10 T. An anomalous increase in the resistance in weak fields is qualitatively consistent with the suppression of the antilocalization correction to the resistance, and the maximum is qualitatively associated with the classical size effect. Near the maximum at temperatures below 0.8 K, manifestations of reproducible magneto-oscillations of the resistance, which are periodic in field, have been detected. The period of these oscillations is close to a value corresponding to the passage of the flux quantum hc/e through the section of a nanowire. The Fourier analysis also confirms that the oscillations are periodic. This result is similar to the manifestation the Aharonov–Bohm effect caused by conducting surface states of Dirac fermions occupying L-valleys of bismuth.

Spiral Modes and the Observation of Quantized Conductance in the Surface Bands of Bismuth Nanowires

When electrons are confined in two-dimensional materials, quantum-mechanical transport phenomena and high mobility can be observed. Few demonstrations of these behaviours in surface spin-orbit bands exist. Here, we report the observation of quantized conductance in the surface bands of 50-nm Bi nanowires. With increasing magnetic fields oriented along the wire axis, the wires exhibit a stepwise increase in conductance and oscillatory thermopower, possibly due to an increased number of high-mobility spiral surface modes based on spin-split bands. Surface high mobility is unexpected since bismuth is not a topological insulator and the surface is not suspended but in contact with the bulk. The oscillations enable us to probe the surface structure. We observe that mobility increases dramatically with magnetic fields because, owing to Lorentz forces, spiral modes orbit decreases in diameter pulling the charge carriers away from the surface. Our mobility estimates at high magnetic fields are comparable, within order of magnitude, to the mobility values reported for suspended graphene. Our findings represent a key step in understanding surface spin-orbit band electronic transport.

Strain-engineered allotrope-like bismuth nanowires for enhanced thermoelectric performance

Allotropy is a fundamental concept that has been frequently studied since the mid-1800s. Although the bulk allotropy of elemental solids is fairly well understood, it remains challenging to reliably produce an allotrope at the nanoscale that has a different crystal structure and accompanies a change in physical properties for specific applications. Here, we demonstrate a "heterostructure" approach to produce allotrope-like bismuth nanowires, where it utilizes the lattice constant difference between bismuth and tellurium in core/shell structure. We find that the resultant strain of [100]-grown Bi nanowires increases the atomic linear density along the c-axis that has been predicted from theoretical considerations, enabling us to establish a design rule for strain-induced allotropic transformation. With our >400-nm-diameter nanowires, we measure a thermoelectric figure of merit ZT of 0.5 at room temperature with reduced thermal conductivity and enhanced Seebeck coefficient, which are primarily a result of the rough interface and the reduced band overlap according to our density-functional calculations.