First-principles study of ZnO cluster-decorated carbon nanotubes

We have investigated the structural, electronic and carbon monoxide (CO) detection properties of the ZnO cluster-decorated single-walled carbon nanotubes (SWCNTs) by using density functional theory (DFT). The stable structures of hybrid ZnO/SWCNT materials are that the ZnO cluster plane is perpendicular to the surface of SWCNTs with the Zn atoms towards the SWCNTs (Zn atom above axial C-C bond or above the C atom). For the ZnO cluster-decorated semiconducting SWCNTs, the SWCNTs present p-type characteristics which may lead to the decrease of conductance upon illumination with ultraviolet (UV) light. The CO can be adsorbed on the hybrid ZnO/SWCNT materials due to the charge transfer between them. Compared with isolated ZnO clusters or bare SWCNTs, the ZnO/SWCNT network would have excellent CO detection ability due to their suitable adsorption energy and conductivity.     

Water-processable polyaniline with covalently bonded single-walled carbon nanotubes: enhanced electrochromic properties and impedance analysis

Hybrid electrochromic materials were readily synthesized via copolymerization of aniline with p-phenylenediamine-functionalized single-walled carbon nanotubes (SWCNTs) in the presence of poly(styrene sulfonate) (PSS) dopant in an aqueous medium. Polyaniline (PANI)-grafted SWCNTs are formed, and they are uniformly dispersed in the PANI/PSS matrix. Impedance analysis shows that the charge-transfer resistances of the hybrids at all states are reduced drastically with increasing SWCNT loading. With 0.8 wt % SWCNTs, the charge-transfer resistances of the hybrid at +1.5 and -1.5 V are only about 20% and 12% of those of PANI/PSS, respectively, which is due to the greatly increased redox reactivity given by the enhanced electron transport in the hybrid and further doping function of the SWCNTs. The remarkable increase in redox reactivity leads to much enhanced electrochromic contrast from 0.34 for PANI to 0.47 for PANI-SWCNT-0.8%.     

Direct discrimination between semiconducting and metallic single-walled carbon nanotubes with high spatial resolution by SEM

Single-walled carbon nanotube (SWCNT) films with a high density exhibit broad functionality and great potential in nanodevices,as SWCNTs can be either metallic or semiconducting in behavior.The films greatly benefit from characterization technologies that can efficiently identify and group SWCNTs based on metallic or semiconducting natures with high spatial resolution.Here,we developed a facile imaging technique using scanning electron microscopy (SEM) to discriminate between semiconducting and metallic SWCNTs based on black and white colors.The average width of the single-SWCNT image was reduced to ～9 nm,～1/5 of previous imaging results.These achievements were attributed to reduced surface charging on the SiO2/Si substrate under enhanced accelerating voltages.With this identification technique,a CNT transistor with an on/off ratio of ＞105 was fabricated by identifying and etching out the white metallic SWCNTs.This improved SEM imaging technique can be widely applied in evaluating the selective growth and sorting of SWCNTs.     

Diameters of single-walled CNTs (SWCNTs) and related nanochemistry and nanobiology

We reviewed and examined recent progresses related to the nanochemistry and nanobiology of signal-walled carbon nanotubes (SWCNTs), focusing on the diameters of SWCNTs and how the diameters affect the interactions of SWCNT with protein and DNA, which underlay more complex biological responses. The diameters of SWCNTs are closely related to the electronic structure and surface chemistry of SWCNTs, and subsequently affect the interaction of SWCNTs with membrane, protein, and DNA. The surfaces of SWCNT with smaller diameters are more polar, and these with large diameters are more hydrophobic. The preference of SWCNT to interact with Trp/Phe/Met residues indicates it is possible that SWCNT may interfere with normal protein-protein interactions. SWCNT-DNA interactions often change DNA conformation. Besides the promising future of using SWCNTs as delivering nanomaterial, thermal therapy, and other biological applications, we should thoroughly examine the possible effects of carbon nanotube on interrupting normal protein-protein interaction network and other genetic effects at the cellular level.     

Diameters of single-walled carbon nanotubes (SWCNTs) and related nanochemistry and nanobiology

We reviewed and examined recent progresses related to the nanochemistry and nanobiology of signal-walled carbon nanotubes (SWCNTs), focusing on the diameters of SWCNTs and how the diameters affect the interactions of SWCNT with protein and DNA, which underlay more complex biological responses. The diameters of SWCNTs are closely related to the electronic structure and surface chemistry of SWCNTs, and subsequently affect the interaction of SWCNTs with membrane, protein, and DNA. The surfaces of SWCNT with smaller diameters are more polar, and these with large diameters are more hydrophobic. The preference of SWCNT to interact with Trp/Phe/Met residues indicates it is possible that SWCNT may interfere with normal protein-protein interactions. SWCNT-DNA interactions often change DNA conformation. Besides the promising future of using SWCNTs as delivering nanomaterial, thermal therapy, and other biological applications, we should thoroughly examine the possible effects of carbon nanotube on interrupting normal protein-protein interaction network and other genetic effects at the cellular level.     

High-performance single-wall carbon nanotube transparent conductive films

A single-wall carbon nanotube(SWCNT) has superior optical,electrical,and mechanical properties due to its unique structure and is therefore expected to be able to form flexible high-performance transparent conductive films(TCFs).However,the optoelectronic performance of these films needs to be improved to meet the requirements of many devices.The electrical resistivity of SWCNTTCFs is mainly determined by the intrinsic resistivity of individual SWCNTs and their junction resistance in networks.We analyze these key factors and focus on the optimization of SWCNTs and their networks,which include the diameter,length,crystallinity and electrical type of the SWCNTs,and the bundle size and interconnects in networks,as well as chemical doping and microgrid design.We conclude that isolated/small-bundle,heavily doped metallic or semiconducting SWCNTs with a large diameter,long length and high crystallinity are necessary to fabricate high-performance SWCNTTCFs.A simple,controllable way to construct macroscopic SWCNT networks with Y-type connections,welded junctions or microgrid design is important in achieving a low resistivity.Finally,some insights into the key challenges in the manufacture and use of SWCNT TCFs and their prospects are presented,hoping to shed light on promoting the practical application of SWCNT TCFs in future flexible and stretchable optoelectronics.     

Polydiacetylene single-walled carbon nanotubes nano-hybrid for cellular imaging applications

The functionalization of single-walled carbon nanotubes (SWCNTs) by forming self-assembled supramolecular structure of 10,12-pentacosadiynoic acid (PCDA) on the carbon nanotube wall is reported. PCDA assemblies on SWCNTs (PCDA/SWCNTs) were polymerized by UV irradiation to extensively conjugated polydiacetylene (PDA). PDA/SWCNT was identified by absorption and emission spectroscopy, scanning and transmission electron microscopies (SEM and TEM) and atomic force microscopy (AFM). PDA/SCWNTs showed strong near-infrared (NIR) fluorescence caused by fluorescence resonance energy transfer (FRET) between PDA network and semiconducting SWCNT core. The micro-patterning of biotinylated PDA/SWCNT with FITC-avidin on biotinylated glass surface demonstrated the potential application for a bio-sensing device. Furthermore, the biocompatibility for mammalian cancer cells was tested by viability experiments, which revealed that the PDA/SWCNTs had very low toxicity below 31.3 mg/L in terms of pristine SWCNTs concentration. Also, PDA/SWCNTs inside the cells can be observed by NIR microscopy. This unique modular method of preparation can contribute to diverse functionalities for practical applications in various non-invasive cellular imaging.     

Comparative analysis of electronic properties of tin,gallium, and bismuth chalcogenide-filled single-walled carbon nanotubes

In the present work, the channels of single-walled carbon nanotubes (SWCNTs) were filled with tin sulfide (SnS), gallium telluride (GaTe), and bismuth selenide (Bi₂Se₃). The successful encapsulation of the compounds was proven by high-resolution transmission electron microscopy. The electronic properties of the filled SWCNTs were studied by optical absorption spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. It was found that the embedded metal chalcogenides have different influence on the electronic properties of the nanotubes. The incorporation of tin sulfide into the SWCNTs does not result in sufficient changes in the electronic structure of SWCNTs, except for a minor influence on metallic nanotubes. The filling of SWCNTs with gallium telluride causes the charge transfer from the SWCNT walls to the encapsulated compound due to acceptor doping of the nanotubes. The insertion of bismuth selenide inside the SWCNT channels does not lead to the modification of the electronic properties of nanotubes.     

Piperidine induced polarity conversion in single-walled carbon nanotube field effect transistors

Piperidine is found to be an efficient electron doping agent that converts as-prepared p-type single-walled carbon nanotube (SWCNT) field effect transistors (FETs) into n-type SWCNT-FETs. Electron transfer from the amine group in piperidine to the SWCNTs is suggested to be the origin of the p- to n-type conversion. The effect of electron doping is further supported by the Raman tangential G(+) and G(-)-peak downshift up to 3 cm(-1) without the peak broadening. No detectable change in the Raman D-peak suggests non-covalent attachment of piperidine to the SWCNTs. A low temperature (110?°C) Si(3)N(4) passivation layer is used to maintain the long term air stability of the converted n-type devices. A complementary SWCNT inverter is demonstrated through integrating the n- and p-type SWCNT-FETs.     

Synthesis and characterization of polyurethane-grafted single-walled carbon nanotubes via click chemistry

Polyurethane (PU)-grafted carbon nanotubes were synthesized by the coupling of alkyne moiety decorated single walled carbon nanotube (SWCNT) with azide moiety containing PU using Cu(I) catalyzed Huisgen [3 + 2] cycloaddition click chemistry. The azide moiety containing poly(s-caprolactone)diol was synthesized by ring-opening polymerization and further used for PU synthesis. Alkyne-functionalizion of SWCNT was completed by the reaction of p-aminophenyl propargyl ether with SWCNT using a solvent free diazotization procedure. Nuclear magnetic resonance, Fourier transform infrared, and Raman spectroscopic measurements confirmed the functionalization of SWCNT. Scanning electron microscopy and transmission electron microscopy images showed an excellent dispersion of SWCNTs, and specially debundling of SWCNTs could be observed due to polymer assisted dispersion. A quantitative grafting was successfully achieved even at high content of functional groups.     

Preparation of single-walled carbon nanotube/silicon composites and their lithium storage properties

Single-walled carbon nanotube (SWCNT)/silicon composites were produced from the purified SWCNTs and Si powder by high-energy ball-milling and then electrochemically inserted with Li using Li/(SWCNT/Si) cells. The highest reversible capacity and lowest irreversible capacity of the SWCNT/Si composites were measured to be 1845 and 474 mAh g(-1) after ball-milling for 60 min, respectively. During the charge/discharge process, most of the Li ions were inserted into the SWCNT/Si composites by alloying with Si particles below 0.2 V and extracted from the SWCNT/Si composites by dealloying with Si particles around 0.5 V. The enhanced capacity and cycle performance of the SWCNT/Si composites produced by high-energy ball-milling were due primarily to the fact that SWCNTs provided a flexible conductive matrix, which compensated for the dimensional changes of Si particles during Li insertion and avoided loosening of the interparticle contacts during the crumbling of Si particles. The ball-milling contributed to a decrease in the particle size of SWCNTs and Si particles and to an increase in the electrical contact between SWCNTs and Si particles in the SWCNT/Si composites.     

The manipulation of carbon nanotubes on a polymer surface using a laser beam

Controlled noninvasive manipulation of porphyrin-doped single-walled carbon nanotubes (SWCNT) by laser beam is described. SWCNT/porphyrin complexes have been deposited on a polymer surface and irradiated by a scanning beam of laser light with the wavelength of 405 nm. Laser energy was absorbed by the porphyrin and converted into heat through an energy transfer within the complexes. This led to periodical deformation of the initially flat polymer surface. As a result of the surface deformation the SWCNTs or SWCNT bundle move in the direction given by the laser scanning. It was proved that SWCNTs can be moved to a desired position using the focused laser beam.     

场离子显微镜观测单壁碳纳米管

场离子显微镜是具有原子级分辨能力的尖端表面分析工具.它适用于纳米尺度的单壁碳纳米管(SWCNTs)末端表面原子排列的观测.利用范氏力将SWCNTs组装到钨针尖上,用场离子显微镜观察了这种针尖样品.在观察过程中对针尖样品进行了加热处理,既除掉非晶的C原子,也破坏了由于碳纳米管切割制造过程使用表面活化剂引起的高电阻层,得到了开口SWCNTs的场离子显微镜像,由此推断出SWCNTs束的顶端原子结构,估算出观察到的SWCNTs的直径,并且模拟了其中一个图像所代表的SWCNTs顶端开口的原子排列,推断出产生这个图像的SWCNTs是(7,7)型结构.     

Theoretical study of the interactions of carbon monoxide with Rh-decorated (8,0) single-walled carbon nanotubes

Recent laboratory studies have shown that metal nanoparticles-decorated single-walled carbon nanotubes (SWCNTs) can be used to detect carbon monoxide (CO) gases at room temperature, which is known not able to be adsorbed on pure SWCNTs. In this paper, we investigated the Rh-decorated (8,0) SWCNT and its interaction with CO gases by using density functional theory (DFT) methods. Upon Rh atom adsorption, the conductivity of the (8,0) SWCNT and the atomic charges of some carbon atoms around Rh atom are enhanced dramatically. The Rh-adsorption may be thought of as providing “activated” carbon-sites of adsorbing foreign species. Both the Rh-site and the “activated” C-sites are considered as reactivity sites for the adsorption of CO gases. The binding energy is larger for CO-adsorption on the Rh-site than on the “activated” C-sites. Since the interaction between CO gases and the Rh-site is very strong, the Rh-decorated SWCNT is not reusable for CO gases detecting due to the large binding energy. On the other hand, the CO gases can also be adsorbed on the “activated” C-site with the binding energy of about −0.80 eV and 0.12 electrons transfer. The electronic properties have changed dramatically upon the CO gases. These calculation results are useful not only to explain the sensing mechanisms but also to evaluate the potential for SWCNTs-based sensing materials at room temperature.     

Effect of oxygen doping on electrical properties of small radius (2,1) single-walled carbon nanotubes

We investigated the electrical conductivity of the small radius oxygen-doped (2,1) single-walled carbon nanotubes (SWCNTs) using first-principles density functional theory (DFT). We found that introduction of oxygen does not significantly change the global structure of the SWCNT, and thus the bonding mode of the structure is not remarkably altered. The results show that doping enhances the conductivity of the SWCNT. Oxygen doping increases density of states at the Fermi level, thus the conductivity of the doped SWCNT increases when oxygen is introduced, consistent with experimental observations. These observations were further clarified by comparing band structures of pristine and doped nanotubes.     

Highly conductive interwoven carbon nanotube and silver nanowire transparent electrodes

Abstract

Electrodes fabricated using commercially available silver nanowires (AgNWs) and single walled carbon nanotubes (SWCNTs) produced sheet resistances in the range 4–24 Ω □^?1 with specular transparencies up to 82 %. Increasing the aqueous dispersibility of SWCNTs decreased the bundle size present in the film resulting in improved SWCNT surface dispersion in the films without compromising transparency or sheet resistance. In addition to providing conduction pathways between the AgNW network, the SWCNTs also provide structural support, creating stable self-supporting films. Entanglement of the AgNWs and SWCNTs was demonstrated to occur in solution prior to deposition by monitoring the transverse plasmon resonance mode of the AgNWs during processing. The interwoven AgNW/SWCNT structures show potential for use in optoelectronic applications as transparent electrodes and as an ITO replacement.     

Mediatorless,Reversible Optical Nanosensor Enabled through Enzymatic Pocket Doping

Single‐walled carbon nanotubes (SWCNTs) exhibit intrinsic near‐infrared fluorescence that benefits from indefinite photostability and tissue transparency, offering a promising basis for in vivo biosensing. Existing SWCNT optical sensors that rely on charge transfer for signal transduction often require exogenous mediators that compromise the stability and biocompatibility of the sensors. This study presents a reversible, mediatorless, near‐infrared glucose sensor based on glucose oxidase‐wrapped SWCNTs (GOx‐SWCNTs). GOx‐SWCNTs undergo a selective fluorescence increase in the presence of aldohexoses, with the strongest response toward glucose. When incorporated into a custom‐built membrane device, the sensor demonstrates a monotonic increase in initial response rates with increasing glucose concentrations between 3 × 10^?3 and 30 × 10^?3m and an apparent Michaelis–Menten constant of K_M(app) ≈ 13.9 × 10^?3m . A combination of fluorescence, absorption, and Raman spectroscopy measurements suggests a fluorescence enhancement mechanism based on localized enzymatic doping of SWCNT defect sites that does not rely on added mediators. Removal of glucose reverses the doping effects, resulting in full recovery of the fluorescence intensity. The cyclic addition and removal of glucose is shown to successively enhance and recover fluorescence, demonstrating reversibility that serves as a prerequisite for continuous glucose monitoring.     

Labeling the defects of carbon nanotubes with thiol groups

Herein, we investigate the reactivity of perfect and defective single-wall carbon nanotubes (SWCNTs) with the SH group using first principle periodic calculations. The presence of Stone–Wales (SW) defect sites significantly increases the reactivity of SWCNTs against the thiol group. The most reactive site for the addition of the SH radical is the single vacancy defect; the sulfur atom reconstructs the SWCNT framework and the hydrogen atom becomes attached to a carbon atom. The cluster model calculations performed for perfect SWCNTs confirmed a very low reactivity with the thiol group, even for the small diameter and metallic SWCNTs. The reaction between the perfect SWCNT and SH results thermodynamically unfavorable. The different reactivities observed for perfect and defective SWCNTs suggest that the SH group can be employed to perform a chemical labeling of the defect sites present in carbon nanotubes. The SH radical group is quite unique because, even though it has an unpaired electron, it does not react with sp ² carbon frameworks, unless they have defects or curvature similar to C60. The results are discussed in terms of the recent experimental investigations about thiolated SWCNTs. We were able to explain the Transmission Electron Microscopy images of thiolated nanotubes and the lack of reactivity at the tips. Finally, we discuss a possible route to synthesize sulfur-doped SWCNTs using thiol groups and their electronic properties.     

Fabrication and electrochemical behavior of single-walled carbon nanotube/graphite-based electrode

An electrochemical method for determining the dihydroxybenzene derivatives on glassy carbon (GC) has been developed. In this method, the performance of a single-walled carbon nanotube (SWCNT)/graphite-based electrode, prepared by mixing SWCNTs and graphite powder, was described. The resulting electrode shows an excellent behavior for redox of 3,4-dihydroxybenzoic acid (DBA). SWCNT/graphite-based electrode presents a significant decrease in the overvoltage for DBA oxidation as well as a dramatic improvement in the reversibility of DBA redox behavior in comparison with graphite-based and glassy carbon (GC) electrodes. In addition, scanning electron microscopy (SEM) and atomic force microscopy (AFM) procedures performed for used SWCNTs.