Structure and Electrical Properties of Ni Nanowire/Multiwalled‐Carbon Nanotube/Amorphous Carbon Nanotube Heterojunctions

A one‐dimensional heterojunction is fabricated and characterized. This heterojunction comprises a Ni nanowire, a multiwalled carbon nanotube (MWCNT), and an amorphous carbon nanotube (a‐CNT). The three components are in an end‐to‐end configuration, and form two MWCNT contacts, namely a Ni/MWCNT and an MWCNT/a‐CNT contact. The interfacial structures of the two contacts show that multiple outer walls in the MWCNT simultaneously contact the Ni nanowire and the a‐CNT, and can simultaneously participate in electrical transport. By investigating the electrical‐transport properties of the heterojunctions, the two contacts to the MWCNT in every heterojunction are found to behave as two diodes connected in series face‐to‐face, at least one of which exhibits the characteristics of a nearly ideal Schottky diode and obeys thermionic‐emission theory, wherein only the image force lowers the Schottky barrier. The appearance of this type of nearly ideal diode is attributed to the good contacts to the multiple outer walls of the MWCNTs realized by the heterojunctions' structures.     

Charge‐Transport Behavior in Aligned Carbon Nanotubes: A Quantum‐Chemical Investigation

Correlated quantum‐chemical calculations are applied to analyze the amplitude of the electronic‐transfer integrals that describe charge transport in interacting carbon nanotubes (CNTs) by investigating the influences of: i) the relative positions of the CNTs, ii) the size of the CNTs, and iii) their chemical impurities. Our results indicate that the mobility of the charge carrier is extremely sensitive to the molecular packing and the presence of chemical impurities. The largest splitting for the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels is in the case of perfectly cofacial conformations where hexagons face hexagons in the dimer structure. We found that the diameter of the CNT determines the type of transporting carrier: for CNTs with large diameters hole transport dominates, while for thin CNTs electron transport dominates. In general, the carrier mobility for the perfect CNTs (n ≥ 3) is less pronounced than that of C₆₀ due to their relatively small strain. B‐ and N‐doped CNTs exhibit considerably larger mobilities owing to the possibility of metallic behavior. These results provide a plausible explanation for the high mobility found experimentally in a field‐effect transistor (FET) made from a large‐area, well‐aligned CNT array. In addition, these hole‐rich and electron‐rich dopants imply potential applications in nanoelectronics.     

Piezoresistive Sensors Based on Carbon Nanotube Films

Piezoresistive effect of carbon nanotube films was investigated by a three-point bending test. Carbon nanotubes were synthesized by hot filament chemical vapor deposition. The experimental results showed that the carbon nanotubes have a striking piezoresistive effect. The relative resistance was changed from 0 to 10.5 X 10-2 and 3.25 X 10-2 for doped and undoped films respectively at room temperature when the microstrain under stress from 0 to 500. The gauge factors for doped and undoped carbon nanotube films under 500 microstrain were about 220 and 67 at room temperature, respectively, exceeding that of polycrystalline silicon (30) at 35 ℃. The origin of the resistance changes in the films may be attributed to a strain-induced change in the band gap for the doped tubes and the defects for the undoped tubes.     

Continuous Band‐Filling Control and One‐Dimensional Transport in Metallic and Semiconducting Carbon Nanotube Tangled Films

Field‐effect transistors that employ an electrolyte in place of a gate dielectric layer can accumulate ultrahigh‐density carriers not only on a well‐defined channel (e.g., a two‐dimensional surface) but also on any irregularly shaped channel material. Here, on thin films of 95% pure metallic and semiconducting single‐walled carbon nanotubes (SWNTs), the Fermi level is continuously tuned over a very wide range, while their electronic transport and absorption spectra are simultaneously monitored. It is found that the conductivity of not only the semiconducting but also the metallic SWNT thin films steeply changes when the Fermi level reaches the edges of one‐dimensional subbands and that the conductivity is almost proportional to the number of subbands crossing the Fermi level, thereby exhibiting a one‐dimensional nature of transport even in a tangled network structure and at room temperature.     

Electrochemical Properties of High‐Power Supercapacitors Using Single‐Walled Carbon Nanotube Electrodes

We have investigated the key factors determining the performance of supercapacitors constructed using single‐walled carbon nanotube (SWNT) electrodes. Several parameters, such as composition of the binder, annealing temperature, type of current collector, charging time, and discharging current density have been optimized for the best performance of the supercapacitor with respect to energy density and power density. We find a maximum specific capacitance of 180 F/g and a measured power density of 20 kW/kg at energy densities in the range from 7 to 6.5 Wh/kg at 0.9 V in a solution of 7.5 N KOH (the currently available supercapacitors have energy densities in the range 6–7 Wh/kg and power density in the range 0.2–5 kW/kg at 2.3 V in non‐aqueous solvents).     

Properties of Carbon Nanotube Fibers Spun from DNA‐Stabilized Dispersions

The fabrication of single‐walled carbon nanotube (CNT) fibers containing (salmon) DNA has been demonstrated. The DNA material has been found to be adequate for dispersing relatively large concentrations (up to 1 % by weight) of carbon nanotubes. These dispersions are better suited for fiber spinning than previously studied dispersions based on conventional surfactants, such as sodium dodecyl sulfate (SDS). The DNA‐containing fibers were less conductive than the fibers based on SDS, but they were significantly stronger. Considerably increased conductivity was obtained by thermally annealing the CNT/DNA fibers, a process accompanied by a loss in mechanical strength. Smaller improvements in conductivity could be introduced by annealing the carbon nanotubes before fiber production, with no alteration of the fiber mechanical properties. Those CNT/DNA fibers that were mechanically strong and conductive also exhibited good electrochemical behavior and useful capacitance values (up to 7.2 F g^–1).     

Carbon Nanotube Biofiber Formation in a Polymer‐Free Coagulation Bath

A novel solution spinning method to produce highly conducting carbon nanotube (CNT) biofibers is reported. In this process, carbon nanotubes are dispersed using biomolecules such as hyaluronic acid, chitosan, and DNA, and these dispersions are used as spinning solutions. Unlike previous reports in which a polymer binder is used in the coagulation bath, these dispersions can be converted into fibers simply by altering the nature of the coagulation bath via pH control, use of a crosslinking agent, or use of a biomolecule‐precipitating solvent system. With strength comparable to most reported CNT fibers to date, these CNT biofibers demonstrate superior electrical conductivities. Cell culture experiments are performed to investigate the cytotoxicity of these fibers. This novel fiber spinning approach could simplify methodologies for creating electrically conducting and biocompatible platforms for a variety of biomedical applications, particularly in those systems where the application of an electrical field is advantageous?for example, in directed nerve and/or muscle repair.     

Shaping Carbon Nanotubes and the Effects on Their Electrical and Mechanical Properties

A method is developed and shown to be able to shape a carbon nanotube (CNT) into a desired morphology while maintaining its excellent electrical and mechanical properties. Single, freestanding nanotubes are bent by a scanning tunneling microscopy probe, and their morphology is fixed by electron‐beam‐induced deposition (inside a transmission electron microscope) of amorphous carbon on the bent area. It is shown that the mechanical strength of the bent CNT may be greatly enhanced by increasing the amount of carbon glue or the deposition area, and the electrical conduction of the nanotube shows hardly any dependence on the bending deformation or on the deposition of amorphous carbon. Our findings suggest that CNTs might be manipulated and processed as interconnections between electronic devices without much degradation in their electrical conductance, and be used in areas requiring complex morphology, such as nanometer‐scale transport carriers and nanoelectromechanical systems.     

Carbon Nanotube Coatings on Bioglass‐Based Tissue Engineering Scaffolds

The coating of highly porous Bioglass^® based 3D scaffolds with multi‐walled carbon nanotubes (CNT) was investigated. Foam like Bioglass^® scaffolds were fabricated by the replica technique and electrophoretic deposition was used to deposit homogeneous layers of CNT throughout the scaffold pore structure. The optimal experimental conditions were determined to be: applied voltage 15 V and deposition time 20 minutes, utilizing a concentrated aqueous suspension of CNT with addition of a surfactant and iodine. The scaffold pore structure remained invariant after the CNT coating, as assessed by SEM. The incorporation of CNTs induced a nanostructured internal surface of the pores which is thought to be beneficial for osteoblast cell attachment and proliferation. Bioactivity of the scaffolds was assessed by immersion studies in simulated body fluid (SBF) for periods of up to 2 weeks and the subsequent determination of hydroxyapatite (HA) formation. The presence of CNTs can enhance the bioactive behaviour of the scaffolds since CNTs can serve as template for the ordered formation of a nanostructured HA layers, which does not occur on uncoated Bioglass^® surfaces.     

Electrochemically Tuned Properties for Electrolyte‐Free Carbon Nanotube Sheets

Injecting high electronic charge densities can profoundly change the optical, electrical, and magnetic properties of materials. Such charge injection in bulk materials has traditionally involved either dopant intercalation or the maintained use of a contacting electrolyte. Tunable electrochemical charge injection and charge retention, in which neither volumetric intercalation of ions nor maintained electrolyte contact is needed, are demonstrated for carbon nanotube sheets in the absence of an applied field. The tunability of electrical conductivity and electron field emission in the subsequent material is presented. Application of this material to supercapacitors may extend their charge‐storage times because they can retain charge after the removal of the electrolyte.     

Temperature‐Dependent Electrical Transport in Polymer‐Sorted Semiconducting Carbon Nanotube Networks

The temperature dependence of the electrical characteristics of field‐effect transistors (FETs) based on polymer‐sorted, large‐diameter semiconducting carbon nanotube networks is investigated. The temperature dependences of both the carrier mobility and the source‐drain current in the range of 78 K to 293 K indicate thermally activated, but non‐Arrhenius, charge transport. The hysteresis in the transfer characteristics of FETs shows a simultaneous reduction with decreasing temperature. The hysteresis appears to stem from screening of charges that are transferred from the carbon nanotubes to traps at the surface of the gate dielectric. The temperature dependence of sheet resistance of the carbon nanotube networks, extracted from FET characteristics at constant carrier concentration, specifies fluctuation‐induced tunneling as the mechanism responsible for charge transport, with an activation energy that is dependent on film thickness. Our study indicates inter‐tube tunneling to be the bottleneck and implicates the role of the polymer coating in influencing charge transport in polymer‐sorted carbon nanotube networks.     

Modifying the Electronic Character of Single‐Walled Carbon Nanotubes Through Anisotropic Polymer Interaction: A Raman Study

Using Raman spectroscopy, we demonstrate that the anisotropic interaction between single‐walled carbon nanotubes (SWNTs) and poly(methyl methacrylate) (PMMA) causes significant changes in the electronic properties of their composites. Two different procedures were used to prepare the composites: melt blending and in‐situ UV polymerization. Resonant Raman studies relate the electronic density of states (DOS) of the SWNTs to the corresponding vibration symmetry changes of both the PMMA and the SWNTs. Our results show that, in the melt‐blended sample, the SWNTs—originally semiconducting—became predominantly metallic. The changes in the electronic properties were also confirmed by dielectric constant measurements. We propose that the anisotropic interaction between PMMA and SWNTs in the melt‐blended composite is the dominant reason for the observed electronic character change.     

玻璃基底上氧化铟锡薄膜的光致发光性能

用直流磁控溅射法在190℃玻璃基底上制备了氧化铟锡(ITO)薄膜,利用荧光分光光度计研究了ITO薄膜的光致发光性能。结果表明,室温下ITO薄膜在波长250 nm光源的激发下,分别在467 nm和751 nm处观察到了发光强度较强的蓝光宽带和强度较弱的红光带。上述发光峰的出现分别和ITO薄膜中的氧空位、铟空位等缺陷在禁带中形成的能级有关,其中氧空位形成的施主能级位于导带下1.2 eV处,而铟空位形成的受主能级位于价带下1.65 eV处。     

Directed Self‐Assembly of Gradient Concentric Carbon Nanotube Rings

Hundreds of gradient concentric rings of linear conjugated polymer, (poly[2‐methoxy‐5‐(2‐ethylhexyloxy)‐1,4‐ phenylenevinylene], i.e., MEH‐PPV) with remarkable regularity over large areas were produced by controlled “stick‐slip” motions of the contact line in a confined geometry consisting of a sphere on a flat substrate (i.e., sphere‐on‐flat geometry). Subsequently, MEH‐PPV rings were exploited as a template to direct the formation of gradient concentric rings of multiwalled carbon nanotubes (MWNTs) with controlled density. This method is simple, cost effective, and robust, combining two consecutive self‐assembly processes, namely, evaporation‐induced self‐assembly of polymers in a sphere‐on‐flat geometry, followed by subsequent directed self‐assembly of MWNTs on the polymer‐templated surfaces.     

Mechanical Properties and Flame‐Retardant Behavior of Ethylene Vinyl Acetate/High‐Density Polyethylene Coated Carbon Nanotube Nanocomposites

High‐density polyethylene coated multiwalled carbon nanotubes (c‐MWNTs) and multiwalled carbon nanotubes (MWNTs) have been dispersed into an ethylene vinyl acetate (EVA) copolymer by mechanical kneading. The effect of c‐MWNTs on tensile properties, thermo‐oxidative degradation, and fire behavior has been studied in comparison with virgin EVA and EVA/MWNTs nanocomposites. Due to the better dispersion of the coated nanotubes, the incorporation of 3 wt % of c‐MWNTs leads to an increase of the Young's modulus, the cohesion of the combustion residues, and a decrease of the peak heat‐release rate.     

生长速率对反应蒸发制备ITO薄膜光电性能的影响

用电阻加热反应蒸发的方法制备氧化铟锡(ITO)薄膜,测试了膜的电阻率、可见光透过率、载流子浓度和迁移率,讨论生长速率对薄膜光电性能的影响.并在衬底温度为160 ℃、反应压强为1.4×10-1 Pa的条件下,制得可见光范围平均透过率为93%、电阻率为4.7×10-4 Ω·cm的ITO透明导电薄膜.     

Strong Carbon‐Nanotube–Polymer Bonding by Microwave Irradiation

The vigorous response of multiwalled carbon nanotubes (MWNTs) to microwave irradiation, leading to the release of a large amount of heat, is used to locally melt a plastic matrix adjacent to the nanotubes within a period of seconds. This results in the intercalation of the MWNTs into the polymer matrix at room temperature without any physical damage to the polymer. The so‐called “microwave welding” approach creates a new paradigm for the formation of very strong MWNT–polymer bonds without the use of any adhesive, and represents a significant step forward for the fabrication of functional nanotube composites. Here, we demonstrate the implications of the anisotropic alignment of MWNTs in polymers, patterned conductors/resistors for soft electronics, and high‐strength composites, where the MWNTs are ‘soldered' to flexible polymer substrates.     

Dibenzothiophene/Oxide and Quinoxaline/Pyrazine Derivatives Serving as Electron‐Transport Materials

A series of 2,8‐disubstituted dibenzothiophene and 2,8‐disubstituted dibenzothiophene‐S,S‐dioxide derivatives containing quinoxaline and pyrazine moieties are synthesized via three key steps: i) palladium‐catalyzed Sonogashira coupling reaction to form dialkynes; ii) conversion of the dialkynes to diones; and iii) condensation of the diones with diamines. Single‐crystal characterization of 2,8‐di(6,7‐dimethyl‐3‐phenyl‐2‐quinoxalinyl)‐5H‐5λ⁶‐dibenzo[b,d]thiophene‐5,5‐dione indicates a triclinic crystal structure with space group P1 and a non‐coplanar structure. These new materials are amorphous, with glass‐transition temperatures ranging from 132 to 194 °C. The compounds (Cpd) exhibit high electron mobilities and serve as effective electron‐transport materials for organic light‐emitting devices. Double‐layer devices are fabricated with the structure indium tin oxide (ITO)/Qn/Cpd/LiF/Al, where yellow‐emitting 2,3‐bis[4‐(N‐phenyl‐9‐ethyl‐3‐carbazolylamino)phenyl]quinoxaline (Qn) serves as the emitting layer. An external quantum efficiency of 1.41 %, a power efficiency of 4.94 lm W^–1, and a current efficiency of 1.62 cd A^–1 are achieved at a current density of 100 mA cm^–2.     

Fabrication and Electrical and Mechanical Properties of Carbon Nanotube Interconnections

Individual carbon nanotubes (CNTs) have been cut, manipulated, and soldered via electron‐beam‐induced deposition of amorphous carbon (a‐C) and using a scanning tunneling microscope inside a transmission electron microscope. All CNT structures, including simple tube–tube connections, crossed junctions, T‐junctions, zigzag structures, and even nanotube networks, have been successfully constructed with a high degree of control, and their electrical and mechanical properties have been measured in situ inside the transmission electron microscope. It is found that multiple CNTs may be readily soldered together with moderate junction resistance and excellent mechanical resilience and strength, and the junction resistance may be further reduced by current‐induced graphitization of the deposited a‐C on the junction.