Solution‐Processing of High‐Purity Semiconducting Single‐Walled Carbon Nanotubes for Electronics Devices

High‐purity semiconducting single‐walled carbon nanotubes (s‐SWCNTs) are of paramount significance for the construction of next‐generation electronics. Until now, a number of elaborate sorting and purification techniques for s‐SWCNTs have been developed, among which solution‐based sorting methods show unique merits in the scale production, high purity, and large‐area film formation. Here, the recent progress in the solution processing of s‐SWCNTs and their application in electronic devices is systematically reviewed. First, the solution‐based sorting and purification of s‐SWCNTs are described, and particular attention is paid to the recent advance in the conjugated polymer‐based sorting strategy. Subsequently, the solution‐based deposition and morphology control of a s‐SWCNT thin film on a surface are introduced, which focus on the strategies for network formation and alignment of SWCNTs. Then, the recent advances in electronic devices based on s‐SWCNTs are reviewed with emphasis on nanoscale s‐SWCNTs' high‐performance integrated circuits and s‐SWCNT‐based thin‐film transistors (TFT) array and circuits. Lastly, the existing challenges and development trends for the s‐SWCNTs and electronic devices are briefly discussed. The aim is to provide some useful information and inspiration for the sorting and purification of s‐SWCNTs, as well as the construction of electronic devices with s‐SWCNTs.     

Purity-enhanced bulk synthesis of thin single-wall carbon nanotubes using iron-copper catalysts

We report high purity and high yield synthesis of single-wall carbon nanotubes (SWCNTs) of narrow diameter from iron-copper bimetal catalysts. The SWCNTs with diameter of 0.8-1.2 nm are synthesized using the zeolite-supported alcohol chemical vapour deposition method. Single metal and bimetal catalysts are systematically investigated to achieve both the enhancement of SWCNT yield and the suppression of the undesired formation of graphitic impurities. The relative yield and purity of SWCNTs are quantified using optical absorption spectroscopy with an ultracentrifuge-based purification technique. For the single metal catalyst, iron shows the highest catalytic activity compared with the other metals such as cobalt, nickel, molybdenum, copper, and platinum. It has been found that the addition of copper to iron results in the suppression of carbonaceous impurity formation without decreasing the SWCNT yield. The purity-enhanced SWCNT shows fairly low sheet resistance due to the improvement of inter-nanotube contacts. This scalable design of SWCNT synthesis with enhanced purity is therefore a promising tool for shaping future high performance devices.     

Single Chirality (6,4) Single‐Walled Carbon Nanotubes for Fluorescence Imaging with Silicon Detectors

Postsynthetic single‐walled carbon nanotube (SWCNT) sorting methods such as density gradient ultracentrifugation, gel chromatography, and electrophoresis have all been inspired by established biochemistry separation techniques designed to separate subcellular components. Biochemistry separation techniques have been refined to the degree that parameters such as pH, salt concentration, and temperature are necessary for a successful separation, yet these conditions are only now being applied to SWCNT separation methodologies. Slight changes in pH produce radically different behaviors of SWCNTs inside a density gradient, allowing for the facile separation of ultrahigh purity (6,4) SWCNTs from as‐synthesized carbon nanotubes. The (6,4) SWCNTs are novel fluorophores emitting below ≈900 nm and can be easily detected with conventional silicon‐based charge‐coupled device detectors without the need for specialized InGaAs cameras. The (6,4) SWCNTs are used to demonstrate their potential as a clinically relevant NIR‐I fluorescence stain for the immunohistochemical staining of cells and cancer tissue sections displaying high endothelial growth factor receptor levels.     

Diketopyrrolopyrrole (DPP)‐Based Donor–Acceptor Polymers for Selective Dispersion of Large‐Diameter Semiconducting Carbon Nanotubes

Low‐bandgap diketopyrrolopyrrole (DPP)‐based polymers are used for the selective dispersion of semiconducting single‐walled carbon nanotubes (s‐SWCNTs). Through rational molecular design to tune the polymer–SWCNT interactions, highly selective dispersions of s‐SWCNTs with diameters mainly around 1.5 nm are achieved. The influences of the polymer alkyl side‐chain substitution (i.e., branched vs linear side chains) on the dispersing yield and selectivity of s‐SWCNTs are investigated. Introducing linear alkyl side chains allows increased polymer–SWCNT interactions through close π–π stacking and improved C–H–π interactions. This work demonstrates that polymer side‐chain engineering is an effective method to modulate the polymer–SWCNT interactions and thereby affecting both critical parameters in dispersing yield and selectivity. Using these sorted s‐SWCNTs, high‐performance SWCNT network thin‐film transistors are fabricated. The solution‐deposited s‐SWCNT transistors yield simultaneously high mobilities of 41.2 cm² V^?1 s^?1 and high on/off ratios of greater than 10⁴. In summary, low‐bandgap DPP donor–acceptor polymers are a promising class of polymers for selective dispersion of large‐diameter s‐SWCNTs.     

Synthesis of individual ultra-long carbon nanotubes and transfer to other substrates

In this article, we report the synthesis of ultra-long carbon nanotubes (CNTs) by thermal chemical vapour deposition method. Ultra-long, individual and aligned CNTs were directly grown on a flat silicon substrate. The orientation of the nanotubes was found parallel to the gas flow direction. The ultra-long CNTs were grown with different transition metallic salts, such as nickel chloride, iron (III) chloride, cobalt acetate and ruthenium acetate, as the catalysts. The influence of the growth conditions, such as growth temperature, reactive gas flow on the length and alignment of the CNTs was studied in detail. By using different catalysts, ultra-long single-walled carbon nanotubes (SWCNTs) or multi-walled carbon nanotubes (MWCNTs) were successfully grown. These ultra-long CNTs were transferred to other substrates by two methods. (1) The first method is to use polydimethylsiloxane as a stamp. (2) The second method is to use KOH as an etching agent. The diameter and length of the CNTs were characterised by transmission electron microscope, scanning electron microscope, atomic force microscope and Raman spectroscopy. The results indicate that the length of the CNTs can reach up to 4?mm. The diameter of the SWCNTs is in the range of 0.7–2.1?nm and the diameter of the MWCNTs is approximately 150?nm.     

Chirality-controlled synthesis of single-walled carbon nanotubes—From mechanistic studies toward experimental realization

Carbon nanotubes (CNTs) have the recorded mechanical strength, exceptionally high thermal stability close to that of diamond, and an extremely high carrier mobility, which is two orders of magnitude higher than that of silicon. A CNT can be conducting, medium or small band gap semiconducting, depending on the exact atomic configuration and the tube diameter. To realize its applications in high-end electronics and even replacing silicon in semiconductor industry, the synthesis of high-purity single-walled CNTs (SWCNTs) with unique structure (chirality) at a relatively low price, is essential. Direct synthesis of SWCNTs with the desired chirality has been one of the great challenges for more than 20?years and it is only very recently that direct synthesis of SWCNTs with purity >90% was achieved. In this review, we have summarized previous researches and state-of-the-art chirality-selective SWCNT synthesis, including experimental and theoretical studies dealing with the mechanism of SWCNT growth, potential routes toward chirality-selection during growth, and recent experimental techniques targeted toward the selective growth of high-purity SWCNTs.     

A novel method to produce large amount single-walled carbon nanotubes by arc discharging

A new method to produce large quantities of single-walled carbon nanotubes (SWCNTs) with high purity is developed. Using several composite graphite rods containing Y and Ni powder as the anode, and a high purity graphite hemisphere as the cathode, a cloth-like deposit could be obtained by dc arc-discharge in helium at high temperature. The deposit contained about 50% SWCNTs. In this way, more than one gram deposit could be produced in a few minutes. The structure and morphology of the SWCNTs were then examined using transmission electron microscopy, Raman spectroscopy, and thermogravimetric analysis. The article is published in the original.     

Self‐Sorting of 10‐µm‐Long Single‐Walled Carbon Nanotubes in Aqueous Solution

Single‐walled carbon nanotubes (SWCNTs) are a class of 1D nanomaterials that exhibit extraordinary electrical and optical properties. However, many of their fundamental studies and practical applications are stymied by sample polydispersity. SWCNTs are synthesized in bulk with broad structural (chirality) and geometrical (length and diameter) distributions; problematically, all known post‐synthetic sorting methods rely on ultrasonication, which cuts SWCNTs into short segments (typically <1 µm). It is demonstrated that ultralong (>10 µm) SWCNTs can be efficiently separated from shorter ones through a solution‐phase “self‐sorting”. It is shown that thin‐film transistors fabricated from long semiconducting SWCNTs exhibit a carrier mobility as high as ≈90 cm² V^?1 s^?1, which is ≈10 times higher than those which use shorter counterparts and well exceeds other known materials such as organic semiconducting polymers (<1 cm² V^?1 s^?1), amorphous silicon (≈1 cm² V^?1 s^?1), and nanocrystalline silicon (≈50 cm² V^?1 s^?1). Mechanistic studies suggest that this self‐sorting is driven by the length‐dependent solution phase behavior of rigid rods. This length sorting technique shows a path to attain long‐sought ultralong, electronically pure carbon nanotube materials through scalable solution processing.     

Length Distribution of Single‐Walled Carbon Nanotubes in Aqueous Suspension Measured by Electrospray Differential Mobility Analysis

The first characterization of the length distribution of single‐walled carbon nanotubes (SWCNT) dispersed in a liquid by electrospray differential mobility analysis (ES‐DMA) is presented. Although an understanding of geometric properties of SWCNTs, including length, diameter, aspect ratio, and chirality, is essential for commercial applications, rapid characterization of nanotube length distributions remains challenging. Here the use of ES‐DMA to obtain length distributions of DNA‐wrapped SWCNTs dispersed in aqueous solutions is demonstrated. Lengths measured by ES‐DMA compare favorably with those obtained from multiangle light scattering, dynamic light scattering, field flow fractionation with UV/vis detection, and atomic force microscopy, validating ES‐DMA as a technique to measure SWCNTs of <250 nm in length. The nanotubes are previously purified and dispersed by wrapping with oligomeric DNA in aqueous solution and centrifuging to remove bundles and amorphous carbon. These dispersions are particularly attractive due to their amenability to bulk processing, ease of storage, high concentration, compatibility with biological and high‐throughput manufacturing environments, and for their potential applications ranging from electronics and hydrogen‐storage vessels to anticancer agents.     

Influence of Mo or Cu doping in Fe/MgO catalyst for synthesis of single-walled carbon nanotubes by catalytic chemical vapor deposition of methane

A series of mono-, bi- or tri-metallic Fe–Mo-Cu/MgO catalysts with the same metal loading of 6 wt% were prepared by impregnation method and used as catalysts for synthesis single-walled carbon nanotubes (SWCNTs) via methane decomposition. XRD, H₂-TPR, and nitrogen physisorption techniques were used to characterize the freshly calcined catalysts, while HRTEM, Raman spectroscopy and TGA were employed to investigate the morphology and microstructure of the SWCNTs product. The obtained results indicated that the introduction of Mo or Cu in the Fe/MgO catalyst enhanced the catalytic growth activity. TEM images showed that both bundles and isolated SWCNTs were obtained over Mo containing catalysts, whereas only SWCNTs bundles were grown over the Fe-Cu/MgO catalyst. The obtained SWCNTs having a diameter of around 0.9–2.4 nm. Raman analysis illustrated that all promoted catalysts produced high quality of SWCNTs compared to the unpromoted Fe/MgO catalyst.     

Selective Growth of Metal‐Free Metallic and Semiconducting Single‐Wall Carbon Nanotubes

A major obstacle for the use of single‐wall carbon nanotubes (SWCNTs) in electronic devices is their mixture of different types of electrical conductivity that strongly depends on their helical structure. The existence of metal impurities as a residue of a metallic growth catalyst may also lower the performance of SWCNT‐based devices. Here, it is shown that by using silicon oxide (SiO_x) nanoparticles as a catalyst, metal‐free semiconducting and metallic SWCNTs can be selectively synthesized by the chemical vapor deposition of ethanol. It is found that control over the nanoparticle size and the content of oxygen in the SiO_x catalyst plays a key role in the selective growth of SWCNTs. Furthermore, by using the as‐grown semiconducting and metallic SWCNTs as the channel material and source/drain electrodes, respectively, all‐SWCNT thin‐film transistors are fabricated to demonstrate the remarkable potential of these SWCNTs for electronic devices.     

High-quality single-walled carbon nanotubes synthesis by hot filament CVD on Ru nanoparticle catalyst

We investigated the single-walled carbon nanotubes (SWCNTs) growth on Ru nanoparticle catalyst via hot filament assisted chemical vapor deposition (HFCVD) with two independent W filaments for the carbon precursor (methane) and the hydrogen dissociation respectively. The Ru nanoparticles were obtained following a two-step strategy. At first the growth substrate is functionalized by silanisation, then a self assembly of a ruthenium porphyrin complex monolayer on pyridine-functionalized metal oxide substrates. We have studied the impact of the filaments power and we optimized the SWCNTs growth temperature. The as grown SWCNTs were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and Raman spectroscopy. It was found that the quality, density and the diameter of SWCNTs depends on the filament and growth temperature. Results of this study can be used to improve the understanding of the growth of SWCNTs by HFCVD.     

Catalyst effect on the preparation of single-walled carbon nanotubes by a modified arc discharge

Single-walled carbon nanotubes (SWCNTs) were prepared by a modified arc discharge furnace using 500?Torr helium as buffer gas at 600?°C. The effect of the catalyst type on the production of SWCNTs was studied by transmission electron microscopy, X-ray diffraction and Raman spectroscopy. The experimental results indicated that the catalyst composition plays an important role in the production rate and purity of the SWCNTs product. Fe-Ni-Mg and Co-Ni powder catalysts demonstrated excellent catalytic effect at a catalyst content of 3?wt%. The soot production rate was up to 15?g/hr and the mean diameter of SWCNTs was about 1.3?nm.     

Solvent Effects on Polymer Sorting of Carbon Nanotubes with Applications in Printed Electronics

Regioregular poly(3‐alkylthiophene) (P3AT) polymers have been previously reported for the selective, high‐yield dispersion of semiconducting single‐walled carbon nanotubes (SWCNTs) in toluene. Here, five alternative solvents are investigated, namely, tetrahydrofuran, decalin, tetralin, m‐xylene, and o‐xylene, for the dispersion of SWCNTs by poly(3‐dodecylthiophene) P3DDT. The dispersion yield could be increased to over 40% using decalin or o‐xylene as the solvents while maintaining high selectivity towards semiconducting SWCNTs. Molecular dynamics (MD) simulations in explicit solvents are used to explain the improved sorting yield. In addition, a general mechanism is proposed to explain the selective dispersion of semiconducting SWCNTs by conjugated polymers. The possibility to perform selective sorting of semiconducting SWCNTs using various solvents provides a greater diversity of semiconducting SWCNT ink properties, such as boiling point, viscosity, and surface tension as well as toxicity. The efficacy of these new semiconducting SWCNT inks is demonstrated by using the high boiling point and high viscosity solvent tetralin for inkjet‐printed transistors, where solvent properties are more compatible with the inkjet printing head and improved droplet formation.     

Ultra-high oxidation resistance of suspended single-wall carbon nanotube bundles grown by an "all-laser" process

Single-wall carbon nanotubes (SWCNTs) were laterally grown on SiO2/Si substrates by means of an "all-laser" growth process. Our "all-laser" process stands out by its exclusive use of the same pulsed UV laser, first, to deposit the CoNi nanocatalyst and, second, to grow SWCNTs through the laser ablation of a pure graphite target. The "all-laser" grown SWCNTs generally self-assemble into bundles (5-15 nm-diam.) sprouting from the CoNi nanocatalyst and laterally bridging the 2 microm gap separating adjacent catalysed electrodes (in either "suspended" or "on-substrate" geometries). A comparative study of the oxidation resistance of both suspended and on-substrate SWCNTs was achieved. The "all-laser" grown SWCNTs were subjected to annealing under flowing oxygen at temperatures ranging from 200 to 1100 degrees C. Systematic scanning electron microscopy observations combined with micro-Raman analyses revealed that more than 20% of suspended nanotubes were still stable at temperatures as high as 900 degrees C under flowing O2 while the on-substrate counterpart were completely burnt out at this temperature. Accordingly, the activation energy, as deduced from the Arrhenius plot, of the suspended SWCNTs is found to be as high as approximately 180 kJ mol(-1) (approximately 9 times higher than that of the on-substrate ones). The high quality (almost defect-free) of the nanotubes synthesized by the "all-laser" approach, their protected tips into the embedded CoNi catalyst nanolayer together with their suspended geometry are thought to be responsible for their unprecedented ultra-high oxidation resistance. This opens up new prospects for the use of these suspended nanotubes into nanodevices that have to operate under highly oxidizing environments.     

CVD-grown horizontally aligned single-walled carbon nanotubes: synthesis routes and growth mechanisms

Single-walled carbon nanotubes (SWCNTs) have attractive electrical and physical properties, which make them very promising for use in various applications. For some applications however, in particular those involving electronics, SWCNTs need to be synthesized with a high degree of control with respect to yield, length, alignment, diameter, and chirality. With this in mind, a great deal of effort is being directed to the precision control of vertically and horizontally aligned nanotubes. In this review the focus is on the latter, horizontally aligned tubes grown by chemical vapor deposition (CVD). The reader is provided with an in-depth review of the established vapor deposition orientation techniques. Detailed discussions on the characterization routes, growth parameters, and growth mechanisms are also provided.     

p-n homo-junction arrays of aligned single walled carbon nanotubes fabricated by selective patterning of polyethyleneimine film

We describe the fabrication and electrical performance of p-n homo-junction diode arrays of horizontally aligned single walled carbon nanotubes (SWCNTs). Horizontally aligned SWCNTs grown on stable temperature-cut quartz with a density of ～ 6 SWCNTs μm(-1) were transferred onto a SiO(2)/Si substrate. After the electrical breakdown, aligned SWCNT field effect transistors (FETs) showed unipolar p-type characteristics with a large current on/off ratio of 10(6) at 1 V and a hole mobility per tube of 1500 cm(2) V(-1) s(-1). Spin-coating of polyethyleneimine (PEI) onto p-type SWCNT FETs showed the n-type transfer characteristics. Patterning of spin-coated PEI film enabled the fabrication of p-n homo-junction arrays of aligned SWCNTs in an easy way, where the rectifying behavior was observed with a rectification ratio of ～ 10(4) at ± 2 V. A comparative study with a p-n homo-junction of random networks of SWCNTs confirmed the advantage of aligned SWCNTs for applications in high performance electronic devices.     

Quantum light signatures and nanosecond spectral diffusion from cavity-embedded carbon nanotubes

Single-walled carbon nanotubes (SWCNTs) are considered for novel optoelectronic and quantum photonic devices, such as single photon sources, but methods must be developed to enhance the light extraction and spectral purity, while simultaneously preventing multiphoton emission as well as spectral diffusion and blinking in dielectric environments of a cavity. Here we demonstrate that utilization of nonpolar polystyrene as a cavity dielectric completely removes spectral diffusion and blinking in individual SWCNTs on the millisecond to multisecond time scale, despite the presence of surfactants. With these cavity-embedded SWCNT samples, providing a 50-fold enhanced exciton emission into the far field, we have been able to carry out photophysical studies for the first time with nanosecond timing resolution. We uncovered that fast spectral diffusion processes (1-3 ns) remain that make significant contributions to the spectral purity, thereby limiting the use of SWCNTs in quantum optical applications requiring indistinguishable photons. Measured quantum light signatures reveal pronounced photon antibunching (g(2)(0) = 0.15) accompanied by side-peak bunching signatures indicative of residual blinking on the submicrosecond time scale. The demonstrated enhanced single photon emission from cavity-embedded SWCNTs is promising for applications in quantum key distribution, while the demonstrated passivation effect of polystyrene with respect to the stability of the optical emission opens a novel pathway toward optoelectronic devices with enhanced performance.     

Effect of defects and loading on prediction of Young��s modulus of SWCNTs

In this paper, the influence of various vacancy and Stone-Wales defects on the Young??s modulus of single-walled carbon nanotubes is investigated via a structural model. Dispersion in experimental results is the motivation for this work. Our results show that the type of method used (loading and boundary condition) for the prediction of the Young??s modulus of SWCNTs is very important for the results. The effect of different types of defects on the Young??s modulus is also studied for zigzag and armchair nanotubes with various aspect ratios (length/diameter). A comparison of our results with those of experimental methods indicates that for the exact prediction of the Young??s modulus of SWCNTs we need to apply the correct conditions.     

Purification of single-walled carbon nanotubes

The discovery of carbon nanotubes (CNTs) created much excitement and stimulated extensive research into the properties of nanometer-scale cylindrical networks. From then on, various methods for the synthesis and characterization of aligned CNTs-both single-walled (SWCNTs) and multi-walled (MWCNTs) by different methods have been hotly pursued. Unfortunately, most methods currently in use produce raw multi component solid products, only a small fraction of which contains carbon nanotubes. The balance of the material is composed of residual catalyst particles (some of which are encased in concentric graphitic shells), fullerenes, other graphitic materials and amorphous carbon. These impurities cause a serious impediment for their detailed characterization and applications. If the carbon nanotube is ever to fulfill its promise as an engineering material, large, high quality aliquots will be required. A number of purification methods involving elimination processes such as physical separation, gas phase and liquid phase oxidation in combination with chemical treatments have been developed for nanotube materials. Though the quantitative determination of purity remains controversial, reported yields are best regarded with an appropriate level of skepticism on the method of assay. In this article, a review is given on the past and recent advances in purification of SWCNTs.