Single-walled Carbon Nanotube Films Research Articles

Universal Sublimation Strategy to Stabilize Single-Metal Sites on Flexible Single-Wall Carbon-Nanotube Films with Strain-Enhanced Activities for Zinc-Air Batteries and Water Splitting.

Single-metal-site catalysts have recently aroused extensive research in electrochemical energy fields such as zinc-air batteries and water splitting, but their preparation is still a huge challenge, especially in flexible catalyst films. Herein, we propose a sublimation strategy in which metal phthalocyanine molecules with defined isolated metal-N4 sites are gasified by sublimation and then deposited on flexible single-wall carbon nanotube (SWCNT) films by means of π-π coupling interactions. Specifically, iron phthalocyanine anchored on the SWCNT film prepared was directly used to boost the cathodic oxygen reduction reaction of the zinc-air battery, showing a high peak power density of 247 mW cm-2. Nickel phthalocyanine and cobalt phthalocyanine were, respectively, stabilized on SWCNT films as the anodic and cathodic electrocatalysts for water splitting, showing a low potential of 1.655 V at 10 mA cm-2. In situ Raman spectra and theoretical studies demonstrate that highly efficient activities originate from strain-induced metal phthalocyanine on SWCNTs. This work provides a universal preparation method for single-metal-site catalysts and innovative insights for electrocatalytic mechanisms.

Ultrasensitive detection of miRNA based on single-walled carbon nanotube@MoS2 field-effect transistor regulated by atomic layer deposition

MicroRNAs (miRNAs) act as diagnostic markers for various diseases, and achieving ultra-sensitive detection of miRNAs has an important effect on early disease diagnosis. Field-effect transistor (FET) biosensor exhibits superior sensitivity compared to conventional clinical detection instruments in detecting biomolecules. However, developing high-sensitive FET biosensors for detecting microRNAs remains challenging. In this study, we developed a FET biosensor using MoS2 and a network film of semiconductor single-walled carbon nanotube (SWCNT) as channel materials. The MoS2 cycles were precisely controlled and optimized by atom layer deposition (ALD), and the optimized 3-cycle device exhibited the best performance. This adjustment is beneficial for enhancing the charge transfer between SWCNT and MoS2, as well as improving the on/off ratio and mobility of FET devices. Additionally, the SWCNT@MoS2 structure offers a larger specific surface area, providing more active binding sites on the sensing interface. These two favorable factors contribute to the realization of linear detection miRNA-21 from 1 × 10−17 to 1 × 10−10 mol L−1 in biosensors. The theoretical detection limit of the biosensor is 1.9 × 10−18 mol L−1. This work develops a novel approach to achieve highly sensitive detection of miRNA for high-performance FET biosensors.

Enhancing thermoelectric performance of single-walled carbon nanotube films by poly(styrene sulfonate acid) dispersing and sequential base treatment

Despite single-walled carbon nanotubes (SWCNTs) have attracted great interest for thermoelectric (TE) conversion, the strong van der Waals forces between SWCNTs cause them to aggregate into bundles with poor dispersibility, which dramatically deteriorates the charge carrier transport, and thereby induces low electrical conductivity and TE power factor. Herein, we report a facile and efficient approach to enhance TE performance of SWCNTs via the addition of poly(styrene sulfonic acid) (PSSH) and sequential base treatment. PSSH is served as a dispersant and dopant to improve the dispersibility of SWCNTs and facilitate charge carrier conduction, contributing to high electrical conductivity of 3749 ± 122 S cm−1 and power factor of 117.7 ± 3.4 μW m−1 K−2 for 20 wt% PSSH/SWCNT composite film. Further base treatment induces partial removal of insulative PSSH and de-doping effect of SWCNTs, which decreases the barriers between adjacent nanotubes junctions and modulates charge carrier transport to synergistically optimize the electrical conductivity and Seebeck coefficient. With fine-tuning base treatment temperature, the PSSH/SWCNT composite film reaches highest power factor of 160.6 ± 7.9 μW m−1 K−2, higher than pristine SWCNTs of 70.2 ± 4.4 μW m−1 K−2. This work demonstrates the feasibility of this approach to boost the TE properties of SWCNTs, exhibiting potential application for high performance renewable energy harvesting.

All-Automated Fabrication of Freestanding and Scalable Photo-Thermoelectric Devices with High Performance.

Flexible photo-thermoelectric (PTE) devices have great application prospects in the fields of solar energy conversion, ultrabroadband light detection, etc. A suitable manufacturing process to avoid the substrate effects as well as to create a narrow transition area between p-n modules for high-performance freestanding flexible PTE devices is highly desired. Herein, an automated laser fabrication (ALF) method is reported to construct the PTE devices with rylene-diimide-doped n-type single-walled carbon nanotube (SWCNT) films. Thewet-compressing approach is developed to improve the thermoelectric power factors and figure of merit (ZT) of the SWCNT hybrid films. Then, the films are cut and patterned automatically to make PTE devices with various structures by the proposed ALF method. The freestanding PTE device with a narrow transition area of ≈2-3 µm between the p and n modules exhibits a high-power density of 0.32 µW cm-2 under the light of 200 mW cm-2, which is among the highest level for freestanding-film-based PTE devices. The results pave the way for the automatic production process of PTE devices for green power generation and ultrabroadband light detection.

Aligned and unaligned single-walled carbon nanotube bilayer films for uncooled infrared sensors

Semiconducting single-walled carbon nanotube (SWCNT) film fabrication using the dip-coating method has successfully produced a unique film with two layers of different morphologies, an upper layer of aligned SWCNT film and a lower layer of non-aligned SWCNT network film. In the upper layer, SWCNTs form SWCNT bundles of several SWCNT thicknesses, and the bundles form thin aligned SWCNT films of 2–7 nm in thickness with parallel and equally spaced bundles of SWCNTs. When a bolometer device with this bilayer film was fabricated on electrodes, the upper aligned SWCNT film was the main conductive path with a low resistivity of about 0.2 Ωcm around room temperature. The alignment film also achieved a high temperature coefficient of resistance (TCR) of more than −5%/K due to its thin thickness, which is hardly affected by the slight metallic SWCNT presence. These excellent properties of a high TCR and low resistance are advantageous for the development of innovative sensor elements.

Stable photothermal conversion in single-walled carbon nanotube device with pn-junction under uniform sunlight irradiation

N-type single-walled carbon nanotube (SWCNT) films with high air stabilities have attracted significant attention for their potential application in SWCNT devices featuring pn-junctions for power generation. However, SWCNT devices must be locally heated or formed into suspended structures to generate a temperature difference and produce output power. In this study, pn-junction SWCNT films were fabricated via vacuum filtration and subsequently attached to a polyimide substrate, enabling the creation of SWCNT devices without the need for suspended structures. Upon uniform irradiation with artificial sunlight, the SWCNT device produced a stable output voltage and short-circuit photocurrent. A thermographic image showed the emergence of a temperature gradient originating from the center of the SWCNT film and extending to the edge of the polyimide substrate. This phenomenon can be attributed to the higher optical absorption of SWCNT films compared to that of polyimide substrates. Consequently, the diffusion of carriers within the device generated an electric potential difference. Therefore, the SWCNT device generated a temperature gradient and yielded output power under uniform sunlight irradiation. These findings may aid in the development of facile and flexible optical devices, including photodetectors and hybrid devices integrating solar cells.

High figure-of-merit of single-walled carbon nanotubes films with metallic type conduction

Carbon nanotubes are promising candidates for thermoelectric power generation because of their one-dimensionality mediated high Seebeck coefficient, high electrical conductivity with added advantages of flexibility, light weight, and scalability. We report the temperature-dependent thermoelectric properties of single-walled carbon nanotube (SWCNTs) films. The SWCNTs films exhibit p-type metallic conduction with high Seebeck coefficient (∼69.5 μVK−1) and moderate electrical conductivity (∼76 Scm−1). The films exhibit low thermal conductivity (∼0.1 Wm−1 K−1) due to phonon scattering at the interjunction region. The synergetic combination of thermoelectric properties resulted in a high figure-of-merit of ∼0.11 at 305 K. A flexible thermoelectric generator based on SWCNTs films mounted on a curved hot surface exhibited an output of 17 mV and 54 μA under a small temperature gradient of 10 K. The present work provides possible avenues for developing wearable SWCNTs based thermoelectric power generation modules for harvesting body heat.

Fast liquid-free patterning of SWCNT films for electronic and optical applications

The development of new approaches to assembling carbon nanotubes in next-level architecture organization is one of the key directions in Nanomaterials Science. Meanwhile, the recent advances in the so-called rational design of thin single-walled carbon nanotube (SWCNT) films promise a significant improvement in the performance of electronic and optical devices. In this study, we propose a fast, efficient, and green method for the fabrication of 2D patterned SWCNT structures. This technique is based on the selective area deposition of SWCNTs synthesized in the aerosol (floating catalyst) CVD process. Such a liquid-free and one-step process beneficially distinguishes from existing alternative methods based on lithography on the filter or post-treatment lithography on already synthesized continuous films. We demonstrate a 12-fold improvement in the performance of patterned mesh-shaped SWCNT films used as transparent electrodes when compared to the continuous film. As a result, the sheet resistance at an overall 90 % transparency in the visible light range value of 62 Ω/□ was achieved. Moreover, transferred onto elastomer, the mesh-shaped SWCNT films were efficiently applied as tunable diffraction gratings in the THz range. We believe the technique proposed extends the possibilities of the aerosol CVD process for utilization in various applications.

Improved Heat Dissipation of Dip-Coated Single-Walled Carbon Nanotube/Mesh Sheets with High Flexibility and Free-Standing Strength for Thermoelectric Generators

Single-walled carbon nanotubes (SWCNTs) are promising thermoelectric materials used in thermoelectric generators (TEGs) to power sensors. However, the limitation of SWCNTs is their high thermal conductivity, which makes it difficult to create a sufficient temperature difference. In this study, we fabricated dip-coated SWCNT/mesh sheets using an SWCNT dispersion. Several types of mesh materials were tested, and the most suitable material was polyphenylene sulfide (PPS). SWCNTs were uniformly deposited on the PPS mesh surface without filling the mesh openings. The SWCNT/PPS mesh sheets exhibited flexibility and free-standing strength. When the edge of the SWCNT/PPS mesh sheets were heated, a higher temperature gradient was produced compared with that of the conventional SWCNT film owing to the increase in heat dissipation. A flexible and free-standing TEG with an area of 1200 mm2, fabricated using SWCNT/PPS mesh sheets, exhibited an output voltage of 31.5 mV and maximum power of 631 nW at a temperature difference of 60 K (Tlow: 320 K). When the TEG was exposed to wind at 3 m/s, temperature difference further increased, and the performance of the TEG increased by a factor of 1.3 for output voltage and 1.6 for maximum power. Therefore, we demonstrated that the TEG’s performance could be improved using SWCNT/PPS mesh sheets.

Narrow band absorption and sensing properties of single-walled carbon nanotubes at terahertz metasurface

Due to their excellent electrical and optical properties, carbon nanotubes have unique application prospects in the field of optoelectronics. In this work the vacuum self-assembly method is used to obtain an isotropic single-walled carbon nanotube film with a thickness of 2 μm by the dispersion of single-walled carbon nanotube powder through vacuum filtration; on the basis of extracting the dielectric parameters of the thin film in a range from 0.4 to 2.0 THz, a novel terahertz metasurface narrowband absorber based on single-walled carbon nanotube films is designed and prepared. This metasurface absorber is composed of square and I-shaped narrow slot resonators. The experimental and simulation results show that the proposed terahertz metasurface absorber exhibits four distinct resonance absorption peaks at 0.65, 0.85, 1.16, and 1.31 THz, respectively, achieving a perfect absorption of up to 90%. The absorption mechanism of this novel multi band terahertz metasurface is elucidated by using the theory of multiple reflection interference. By setting analytical layers with different refractive indices on the surface of metasurface device, the sensing performance of metasurface acting as refractive index sensor is studied in depth. The research results indicate that this new type of metasurface absorber has high sensitivity for refractive index sensing, providing new ideas and solutions for further developing carbon-based new terahertz metasurface absorbers.

Preparation and properties of single-walled carbon nanotube/polyetherimide electromagnetic shielding film

In practical applications, flexibility, lightweight, and high performance are the characteristics that polymer-based electromagnetic shielding materials should have. At present, it is still a great challenge to prepare polymer-based electromagnetic shielding materials with excellent conductivity, electromagnetic shielding properties, and mechanical properties. Therefore, in this work, single-walled carbon nanotubes/polyetherimide composite films are prepared by electrostatic spinning and vacuum-assisted filtration through using single-walled carbon nanotubes and polyetherimide as raw materials. By regulating the surface density of single-walled carbon nanotubes, the conductivity of the composite film can be enhanced to 1866 S/cm. For the electromagnetic shielding performance, the total electromagnetic shielding effectiveness of single-walled carbon nanotubes/polyetherimide composite film in Ku band (12–18 GHz) is in a range of 75.78–81.83 dB, which is higher than that of pure single-walled carbon nanotube film (65.19–69.81 dB). This is attributed to the formation of interfaces between the polyetherimide fibers and the single-walled carbon nanotubes, with more interfaces consuming more electromagnetic wave energy for a given range of single-walled carbon nanotube surface densities. For the mechanical properties, the maximum tensile strength and elongation at the break of the single-walled carbon nanotube/polyetherimide film are 1.13 and 1.5 times higher than those of the single-walled carbon nanotube film, with the values of 28.52 MPa and 7.91%, respectively. As the surface density of single-walled carbon nanotubes increases, the interaction between single-walled carbon nanotubes as well as the interaction between polyetherimide fibers and single-walled carbon nanotubes at the interface plays a role in enhancing the mechanical properties of the composite films. The single-walled carbon nanotube/polyetherimide composite films, as an excellent polymer-based electromagnetic shielding composite material, can be used in fields such as the protection of precision electronic instruments and wearable electronic devices.

A new type of portable pohotoelectrochemical sensor with polarity-switchable photocurrent for dopamine detection

The construction of accurate sensing method for dopamine (DA) is significant for the early diagnosis of some neurological diseases. Previous studies show that the concentration of DA in human body ranges from a few pM to several mM, depending on the sample species. Herein, a portable and sensitive photoelectrochemical (PEC) sensor for DA detection has been constructed, which is homogeneously deposited by thiophene-doped graphitic carbon nitride on the films of single-walled carbon nanotubes via vacuum filtration. In contrast to other PEC sensors for DA detections, our sensor shows polarity-switchable photocurrent with increasing DA concentration. Based on the polarity-switchable current response, the proposed PEC sensor exhibits good selectivity and a relatively wide detection range of 2.5-50 μM with the detection limit of 0.36 μM for DA. Furthermore, the applicability of the sensor was also tested for biological samples. The proposed PEC sensor holds much better potential applications in on-site disease monitoring.

SWCNT-Si photodetector with voltage-dependent active surface

New works on Carbon Nanotubes-Silicon MIS heterostructures showed that the presence of thickness inhomogeneities in the insulating layer across the device can be exploited to increase their functionalities. In this work, we report the fabrication and characterization of a device consisting of a Single-Walled Carbon Nanotube (SWCNT) film onto an n-type silicon substrate where the nitride interlayer between the nanotubes and the silicon has been intentionally etched to obtain different thicknesses. Three different silicon nitride thicknesses allow the formation of three regions, inside the same device, each with different photocurrents and responsivity behaviors. We show that by selecting specific biases, the photoresponse of the regions can be switched on and off. This peculiar behavior allows the device to be used as a photodetector with a voltage-dependent active surface. Scanning photo response imaging of the device surface, performed at different biases, highlights this behavior.

Interface Engineering for High-Performance Thermoelectric Carbon Nanotube Films.

Carbon nanotubes (CNTs) stand out for their exceptional electrical, thermal, and mechanical attributes, making them highly promising materials for cutting-edge, lightweight, and flexible thermoelectric applications. However, realizing the full potential of advanced thermoelectric CNTs requires precise management of their electrical and thermal characteristics. This study, through interface optimization, demonstrates the feasibility of reducing the thermal conductivity while preserving robust electrical conductivity in single-walled CNT films. Our findings reveal that blending two functionalized CNTs offers a versatile method of tailoring the structural and electronic properties of CNT films. Moreover, the modified interface exerts a substantial influence over thermal and electrical transfer, effectively suppressing heat dissipation and facilitating thermoelectric power generation within CNT films. As a result, we have successfully produced both p- and n-type thermoelectric CNTs, attaining impressive power factors of 507 and 171 μW/mK2 at room temperature, respectively. These results provide valuable insights into the fabrication of high-performance thermoelectric CNT films.

Effects of preparation method on thermoelectric properties of poly(aniline‐co‐3,4‐ethylenedioxythiophene)/SWCNT composites

AbstractComposites of conducting polymer and single‐walled carbon nanotubes (SWCNTs) are attracting great attentions in harvesting low‐grade waste heat. Prefabricated SWCNTs film used as the working electrode was placed at the liquid interface between the inorganic phase (dilute sulfuric acid solution) and the organic phase consisting of dichloromethane (DCM), aniline (ANI), and 3,4‐ethylenedioxythiophene (EDOT), together with a platinum wire (the counter electrode) and a silver chloride (AgCl/Ag) electrode (the reference electrode), to perform electrochemical polymerization of ANI and EDOT at the liquid interface. Thermoelectric (TE) composites of poly(ANI‐co‐EDOT) and SWCNTs were produced. Compared with composites from ultrasonic mixing and coating methods, the 10 wt% SWCNTs‐composites in situ formed in electrochemical polymerization have the highest power factor (PF) of 41.56 ± 3.58 μW m−1 K−2, higher than the PF values of the composites formed by other two methods. The work indicates that the TE properties of ANI‐EDOT copolymer/SWCNT (poly[ANI‐co‐EDOT]/SWCNT) composites prepared by electrochemical polymerization were better than those of the composites obtained by physical mixing the electrochemically synthesized poly(ANI‐co‐EDOT) with SWCNTs. Moreover, SWCNTs treated with sodium dodecylbenzene sulfonate (SDBS) could further improve the TE properties of the composites.

Acid-base engineered strategy of HKUST-1 dopants for high electrical conductivity of single-walled carbon nanotubes films

The improvement of electrical conductivity of carbon nanotubes is still a challenge via tuning the carrier concentration and mobility with organic or inorganic dopants due to low doping efficiency. In this paper, single-walled carbon nanotubes (SWCNTs) have been doped with Cu3(BTC)2·(H2O)3 (HKUST-1) as metal organic frameworks via simple mixing and vacuum filtration method. With fine acid or base post-treatment, the crystal structure of HKUST-1 was broken into fragments with more active sites and provided plenty of carriers injecting into SWCNTs. The electrical conductivity of SWCNTs/HKUST-1 films was increased by almost 2.5 times compared to pristine SWCNTs at room temperature. The defect tuning of dopants on SWCNTs surface is an effective carrier injection strategy, which provides a way to improve the electrical conductivity of SWCNTs.

Pyridine-mediated B–B bond cleavage of tetrahydroxydiboron to synthesize n-doped SWCNTs with long-term air stability

Neutral radicals, including carbon radicals, are highly useful chemical species for the functionalization of semiconducting materials to change their electrical and optical properties owing to their high reactivity. However, boron radicals have been limited to synthetic and reaction chemistry, with rare utilization in materials science. In this study, a mixture of tetrahydroxydiboron (B2(OH)4) and pyridine derivatives was found to act as an electron dopant for single-walled carbon nanotubes (SWCNTs) because of the electron transfer from pyridine-mediated boron radicals generated by B–B bond dissociation to neutral radicals. In particular, the radical formed from a mixture of B2(OH)4 and 4-phenylpyridine ((4-Phpy)B(OH)2·) efficiently doped electrons into the SWCNT films; thus, n-type SWCNTs with long-term air stability for more than 50 days at room temperature were prepared. Furthermore, the experimental and theoretical surface analyses revealed that the formation of stable cations from ((4-Phpy)B(OH)2·) and the efficient interaction with SWCNTs due to their high planarity served as the mechanism for their stable doping.

Process controlled microstructure of polyvinylidene fluoride/functionalized single walled carbon nanotube composites

AbstractPolyvinylidene fluoride (PVDF)‐functionalized single walled carbon nanotube (FSWCNT) film composites were prepared by two different process conditions—air drying and vacuum drying. Though reports on –PVDF‐FSWCNT composites are available, we provide a new outlook here, which is based on optimized functionalization and novel processing conditions. The microstructural and phase changes occurring in PVDF having nanotubes functionalized for different extent of time were investigated and confirmed that those functionalized for 4 h (FSWCNAT‐4) create polar γ phase in PVDF with improved mechanical and electrical properties. X‐ray photoelectron spectroscopy studies showed that PVDF/FSWCNT‐4 composites have the maximum percentage of functional groups. It is also found that PVDF/FSWCNT‐4 composite films prepared through air drying were rough and had a cloudy appearance suitable for applications demanding open porous structures, whereas those prepared through vacuum drying process were smooth and homogeneous with high optical transparency, suitable for microelectronic applications. Thus, by suitably controlling the processing conditions and by using optimally functionalized nanotubes, PVDF films with multifunctional properties could be achieved. In order to extract the full capabilities of PVDF/SWCNT films, functionalization of the nanotube together with processing conditions plays a significant role.

Single-walled carbon nanotube coated with Ponceau4R-doped over-oxidized polypyrrole as a sensitive sensor for voltammetric monitoring of salbutamol

A sensitive voltammetric sensor is fabricated by the electrochemical oxidation of polypyrrole (PPy) on a glassy carbon electrode surface covered with a thin film of single-walled carbon nanotubes (SWCNT/GCE). Ponceau4R (P4R) used as an anionic dopant controlled the structure, stability, conductivity, and electrochemical properties of the PPy. The porosity and oxygen-containing active sites on the P4R-PPy/SWCNT/GCE were increased by over-oxidation of the PPy layer to achieve P4R-oPPY/SWCNT/GCE. Morphology features of the P4R-oPPY/SWCNT layer are thoroughly characterized using microscopy instruments. The salbutamol (SAL) voltammetric behavior is evaluated by P4R-oPPY/SWCNT/GCE and a mechanism for its electrochemical oxidation is proposed. Optimizing the important parameters in the electrode modification procedure, including the amount of SWCNT and electrochemically deposited P4R-oPPY, and SAL sensing steps such as the solution pH, potential and accumulation time of SAL are optimized precisely. At the best condition, a ~ 20 times enhancement of the SAL oxidation current was observed by P4R-oPPY/SWCNT modifier. Using P4R-oPPY/SWCNT/GCE, a wide two-part linear range of 0.02–10 μM with a detection limit of 6 nM is resulted in the electrochemical measurement of SAL. The P4R-oPPY/SWCNT/GCE with good reproducibility and stability succeeded in correctly measuring SAL in pharmaceutical and clinical samples.

Single-Step Fabrication of Iron Single-Walled Carbon Nanotube Film from Ferrocene as a Conductive-Electrocatalyst Interlayer in Lithium–Sulfur Batteries

Single-Step Fabrication of Iron Single-Walled Carbon Nanotube Film from Ferrocene as a Conductive-Electrocatalyst Interlayer in Lithium–Sulfur Batteries