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.     

Preparation of Homogeneously Dispersed Multiwalled Carbon Nanotube/Polystyrene Nanocomposites via Melt Extrusion Using Trialkyl Imidazolium Compatibilizer

Well‐dispersed multiwalled carbon nanotube (MWNT)/polystyrene nanocomposites have been prepared via melt extrusion, using trialkylimidazolium tetrafluoroborate‐compatibilized MWNTs. Quantification of the improvement is realized via transmission electron microscopy and laser scanning confocal microscopy image analysis. Differential scanning calorimetry and Fourier‐transform infrared and X‐ray diffraction analysis show evidence for a π‐cation, nanotube–imidazolium interaction and the conversion from an interdigitated bilayer, for the imidazolium salt, to an ordered lamellar structure, for the imidazolium on the surface of the MWNTs.     

Mechanical Reinforcement of Polyethylene Using Polyethylene‐Grafted Multiwalled Carbon Nanotubes

The incorporation of carbon nanotubes to a polymer generally improves the stiffness and strength of the polymer, but the ductility and toughness of the polymer are compromised in most cases. Here we report the mechanical reinforcement of polyethylene (PE) using polyethylene‐grafted multiwalled carbon nanotubes (PE‐g‐MWNTs). The stiffness, strength, ductility and toughness of PE are all improved by the addition of PE‐g‐MWNTs. The grafting of PE onto MWNTs enables the well‐dispersion of nanotubes in the PE matrix and improves MWNT/PE interfacial adhesion. The grafting was achieved by a reactive blending process through melt blending of PE containing 0.85 wt % of maleic anhydride and amine‐functionalized MWNTs. The reaction between maleic anhydride and amine groups, as evidenced by X‐ray photoelectron spectroscopy and Raman spectroscopy, leads to the grafting of PE onto the nanotubes.     

Tuning Optoelectronic Properties of Ambipolar Organic Light‐ Emitting Transistors Using a Bulk‐Heterojunction Approach

Bulk‐heterojunction engineering is demonstrated as an approach to producing ambipolar organic light‐emitting field‐effect transistors with tunable electrical and optoelectronic characteristics. The electron and hole mobilities, as well as the electroluminescence intensity, can be tuned over a large range by changing the composition of a bimolecular mixture consisting of α‐quinquethiophene and N,N′‐ditridecylperylene‐3,4,9,10‐tetracarboxylic‐diimide. Time‐resolved photoluminescence spectroscopy reveals that the phase segregation of the two molecules in the bulk heterojunction and their electronic interaction determine the optoelectronic properties of the devices. The results presented show that the bulk‐heterojunction approach, which is widely used in organic photovoltaic cells, can be successfully employed to select and tailor the functionality of field‐effect devices, including ambipolar charge transport and light emission.     

Elaboration of P3HT/CNT/PCBM Composites for Organic Photovoltaic Cells

This Full Paper focuses on the preparation of single‐walled or multi‐walled carbon nanotube solutions with regioregular poly(3‐hexylthiophene) (P3HT) and a fullerene derivative 1‐(3‐methoxycarbonyl) propyl‐1‐phenyl[6,6]C₆₁ (PCBM) using a high dissolution and concentration method to exactly control the ratio of carbon nanotubes (CNTs) to the P3HT/PCBM mixture and disperse the CNTs homogeneously throughout the matrix. The CNT/P3HT/PCBM composites are deposed using a spin‐coating technique and characterized by absorption and fluorescence spectroscopy and by atomic force microscopy to underline the structure and the charge transfer between the CNTs and P3HT. The performance of photovoltaic devices obtained using these composites as a photoactive layer mainly show an increase of the short circuit current and a slight decrease of the open circuit voltage which generally leads to an improvement of the solar cell performances to an optimum CNT percentage. The best results are obtained with a P3HT/PCBM (1 : 1) mixture with 0.1 wt % multi‐walled carbon nanotubes with an open circuit voltage (V_oc) of 0.57 V, a current density at the short‐circuit (I_sc) of 9.3 mA cm^–2 and a fill factor of 38.4 %, which leads to a power conversion efficiency of 2.0 % (irradiance of 100 mW cm^–2 spectroscopically distributed following AM1.5).     

Platinum Nanoparticle Clusters Immobilized on Multiwalled Carbon Nanotubes: Electrodeposition and Enhanced Electrocatalytic Activity for Methanol Oxidation

3D flowerlike Pt nanoparticle clusters are electrodeposited onto multiwalled carbon nanotubes (MWCNTs) by using a three‐step protocol, which is all‐electrochemical and involves a key, second step of a potential pulse sequence. This 3D fractal morphology is in marked contrast to the 2D uniform nanoparticle dispersion of MWCNTs, which is achieved when the second step adopts cyclic voltammetry instead of a potential‐step method. The former is found to exhibit significantly higher electrocatalytic activity and better stability than the latter for oxidation of methanol. These attractive features are attributable to the unique 3D flowerlike structure of Pt nanoparticle clusters on MWCNTs with much higher electrochemically active surface areas. Our work points to a new path for the preparation of 3D Pt/MWCNT nanocomposites, which are promising as electrocatalysts in direct methanol fuel cells.     

Luminescence of Functionalized Carbon Nanotubes as a Tool to Monitor Bundle Formation and Dissociation in Water: The Effect of Plasmid‐DNA Complexation

Functionalized carbon nanotubes (f‐CNTs) are explored as novel nanomaterials for biomedical applications. UV‐vis luminescence of aqueous dispersions of CNT–NH₃⁺ and CNT–NH–Ac (NH–Ac: acetamido) is observed using standard laboratory spectrophotometric instrumentation, and the measured fluorescence intensity is correlated with the aggregation state of the f‐CNTs: a high intensity indicates improved f‐CNT individualization and dispersion, while a decrease in fluorescence intensity indicates a higher degree of nanotube aggregation and bundling as a result of varying the sodium dodecyl sulfate (SDS) concentrations and pH in the aqueous phase. Moreover, utilization of this relationship between fluorescence intensity and the state of f‐CNT aggregation is carried out to elucidate the interactions between f‐CNTs and gene‐encoding plasmid DNA (pDNA). pDNA is shown to interact with CNT–NH₃⁺ primarily through electrostatic interactions that lead concomitantly to a higher degree of f‐CNT bundling. The CNT–NH₃⁺/pDNA interactions are successfully competed by SDS/f‐CNT surface interactions, resulting in the displacement of pDNA. These studies provide exemplification of the use of fluorescence spectrophotometry to accurately describe the aggregation state of water‐soluble f‐CNTs. Characterization of the complexes between pDNA and f‐CNTs elucidates the opportunities and limitations of such supramolecular systems as potential vectors for gene transfer.     

Selective Crystallization of Organic Semiconductors on Patterned Templates of Carbon Nanotubes

A method of patterning large arrays of organic single crystals is reported. Using single‐walled carbon nanotube (SWNT) bundles as patterned templates, several organic semiconductor materials were successfully patterned, including p‐type pentacene, tetracene, sexiphenylene, and sexithiophene, as well as n‐type tetracyanoquinodimethane (TCNQ). This study suggests that the selective growth of crystals onto patterned carbon nanotubes is most likely due to the coarse topography of the SWNT bundles. Moreover, we observed that the crystals nucleated from SWNT bundles and grew onto SWNT bundles in a conformal fashion. The dependence of the number of crystals on the quantity of SWNT bundles is also discussed. The crystal growth can be directly applied onto transistor source‐drain electrodes and arrays of organic single‐crystal field effect transistors are demonstrated. The results demonstrate the potential of utilizing carbon nanotubes as nucleation templates for patterning a broad range of organic materials for applications in optoelectronics.     

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.     

In Situ Growth of Mesoporous SnO2 on Multiwalled Carbon Nanotubes: A Novel Composite with Porous‐Tube Structure as Anode for Lithium Batteries

A novel mesoporous‐nanotube hybrid composite, namely mesoporous tin dioxide (SnO₂) overlaying on the surface of multiwalled carbon nanotubes (MWCNTs), was prepared by a simple method that included in situ growth of mesoporous SnO₂ on the surface of MWCNTs through hydrothermal method utilizing Cetyltrimethylammonium bromide (CTAB) as structure‐directing agents. Nitrogen adsorption–desorption, X‐ray diffraction and transmission electron microscopy analysis techniques were used to characterize the samples. It was observed that a thin layer tetragonal SnO₂ with a disordered porous was embedded on the surface of MWCNTs, which resulted in the formation of a novel mesoporous‐nanotube hybrid composite. On the base of TEM analysis of products from controlled experiment, a possible mechanism was proposed to explain the formation of the mesoporous‐nanotube structure. The electrochemical properties of the samples as anode materials for lithium batteries were studied by cyclic voltammograms and Galvanostatic method. Results showed that the mesoporous‐tube hybrid composites displayed higher capacity and better cycle performance in comparison with the mesoporous tin dioxide. It was concluded that such a large improvement of electrochemical performance within the hybrid composites may in general be related to mesoporous‐tube structure that possess properties such as one‐dimensional hollow structure, high‐strength with flexibility, excellent electric conductivity and large surface area.     

Efficient Load Transfer to Polymer‐Grafted Multiwalled Carbon Nanotubes in Polymer Composites

Multiwalled carbon nanotubes (MWNTs) grafted with poly(methyl methacrylate) (PMMA) were synthesized by emulsion reactions and used as a reinforcement for commercial PMMA. Both scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed that the applied tensile load on the composites was transferred to the PMMA‐grafted MWNTs, leading to a strain failure of the MWNTs rather than an adhesive failure between the MWNTs and the matrix. Dynamic mechanical analysis (DMA) data showed that the storage modulus at 20 °C of the PMMA composite containing 20 wt.‐% of the PMMA‐grafted MWNTs was significantly enhanced by ～ 29 GPa (or by ～ 1100 %) as compared with commercial PMMA.     

Preparation of Short Carbon Nanotubes and Application as an Electrode Material in Li‐Ion Batteries

A new approach is developed for cutting conventional micrometer‐long entangled carbon nanotubes (CNTs) to short ca. 200 nm long segments with excellent dispersion. CNTs with different lengths are used as anode materials in Li‐ion batteries. The reversible capacity of the Li‐ion batteries is increased and the irreversible capacity is decreased upon shortening the length of the CNTs. The reason for this is that the insertion/extraction of Li ions is easier into/from short CNTs as compared to long CNTs because of the shortened length and the presence of lateral defects. Moreover, short CNTs have a lower electrical resistance and Warburg prefactor, resulting in better rate performance at high current densities. The present study suggests that short segments of CNTs obtained by cutting long CNTs may possess novel properties that may be useful for a wide variety of applications.     

Inside Front Cover: High‐Performance and Stable Organic Thin‐Film Transistors Based on Fused Thiophenes (Adv. Funct. Mater. 3/2006)

A series of new organic semiconductors for organic thin‐film transistors using dithieno[3,2‐b:2′,3′‐d]thiophene as the core have been synthesized. In work reported by Liu, Zhu, and co‐workers on p. 426, the phenyl‐substituted compound exhibited a high mobility of 0.42 cm² V^–1 s^–1 and an on/off ratio of 5 × 10⁶. Weekly shelf‐life tests of the transistors based on the bis(diphenyl)‐substituted thiophene under ambient conditions showed that the mobility was almost unchanged after more than two months, demonstrating potential for applications in future organic electronics. A series of new organic semiconductors for organic thin‐film transistors (OTFTs) using dithieno[3,2‐b:2′,3′‐d]thiophene as the core are synthesized. Their electronic and optical properties are investigated using scanning electron microscopy (SEM), X‐ray diffraction (XRD), UV‐vis and photoluminescence spectroscopies, thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC). The compounds exhibit an excellent field‐effect performance with a high mobility of 0.42 cm² V^–1 s^–1 and an on/off ratio of 5 × 10⁶. XRD patterns reveal these films, grown by vacuum deposition, to be highly crystalline, and SEM reveals well‐interconnected, microcrystalline domains in these films at room temperature. TGA and DSC demonstrate that the phenyl‐substituted compounds possess excellent thermal stability. Furthermore, weekly shelf‐life tests (under ambient conditions) of the OTFTs based on the phenyl‐substituted compounds show that the mobility for the bis(diphenyl)‐substituted thiophene was almost unchanged for more than two months, indicating a high environmental stability.     

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.     

Selective Electrochemical Etching of Single‐Walled Carbon Nanotubes

Single‐walled carbon nanotubes (SWNTs) are a promising material for future nanotechnology. However, their applications are still limited in success because of the co‐existence of metallic SWNTs and semiconducting SWNTs produced samples. Here, electrochemical etching, which shows both diameter and electrical selectivity, is demonstrated to remove SWNTs. With the aid of a back‐gate electric field, selective removal of metallic SWNTs is realized, resulting in high‐performance SWNT field‐effect transistors with pure semiconducting SWNT channels. Moreover, electrochemical etching is realized on a selective area. These findings would be valuable for research and the application of SWNTs in electrochemistry and in electronic devices.     

Extracting Parameters from the Current–Voltage Characteristics of Organic Field‐Effect Transistors

Organic field‐effect transistors were fabricated with vapor‐deposited pentacene on aluminum oxide insulating layers. Several methods are used in order to extract the mobility and threshold voltage from the transfer characteristic of the devices. In all cases, the mobility is found to depend on the gate voltage. The first method consists of deriving the drain current as a function of gate voltage (transconductance), leading to the so‐called field‐effect mobility. In the second method, we assume a power‐law dependence of the mobility with gate voltage together with a constant contact resistance. The third method is the so‐called transfer line method, in which several devices with various channel length are used. It is shown that the mobility is significantly enhanced by modifying the aluminum oxide layer with carboxylic acid self‐assembled monolayers prior to pentacene deposition. The methods used to extract parameters yield threshold voltages with an absolute value of less than 2 V. It is also shown that there is a shift of the threshold voltage after modification of the aluminum oxide layer. These features seem to confirm the validity of the parameter‐extraction methods.     

Carbon Nanotube Based Multifunctional Ambipolar Transistors for AC Applications

Field‐effect transistors (FETs) fabricated on large diameter carbon nanotubes (CNTs) present typical ambipolar transfer characteristics owing to the small band‐gap of CNTs. Depending on the DC biasing condition, the ambipolar FET can work in three different regions, and then can be used as the core to realize multifunctional AC circuits. The CNT FET based circuits can work as a high‐efficiency ambipolar frequency doubler in the ambipolar transfer region, and also can function as in‐phase amplifier and inverted amplifier in the linear transfer region. Due to current saturation of the CNT FET, an AC amplifier with a voltage gain of 2 is realized when the device works in the linear transfer region. Achieving an actual amplification and frequency doubling functions indicates that complicated radio frequency circuits or systems can be constructed based on just one kind of device: ambipolar CNT FETs.     

碳纳米管阴极平板显示器的工艺研究

碳纳米管场致发射显示器是一种新型的真空器件，也是一种具有巨大应用潜力的平板型显示设备。本文详细地介绍了碳纳米管场致发射原理，给出了碳纳米管阴极平板显示器的基本结构和工作原理，对于显示器件的真空封装，碳纳米管阴极装配，控制栅极制作等工艺问题进行了阐述和研究。采用这些技术，已经研制出了碳纳米管阴极场致发射显示器的样品。     

High‐Performance and Stable Organic Thin‐Film Transistors Based on Fused Thiophenes

A series of new organic semiconductors for organic thin‐film transistors (OTFTs) using dithieno[3,2‐b:2′,3′‐d]thiophene as the core are synthesized. Their electronic and optical properties are investigated using scanning electron microscopy (SEM), X‐ray diffraction (XRD), UV‐vis and photoluminescence spectroscopies, thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC). The compounds exhibit an excellent field‐effect performance with a high mobility of 0.42 cm² V^–1 s^–1 and an on/off ratio of 5 × 10⁶. XRD patterns reveal these films, grown by vacuum deposition, to be highly crystalline, and SEM reveals well‐interconnected, microcrystalline domains in these films at room temperature. TGA and DSC demonstrate that the phenyl‐substituted compounds possess excellent thermal stability. Furthermore, weekly shelf‐life tests (under ambient conditions) of the OTFTs based on the phenyl‐substituted compounds show that the mobility for the bis(diphenyl)‐substituted thiophene was almost unchanged for more than two months, indicating a high environmental stability.     

Cover Picture: n‐Channel,Ambipolar, and p‐Channel Organic Heterojunction Transistors Fabricated with Various Film Morphologies (Adv. Funct. Mater. 3/2007)

Simultaneous introduction of short‐range repulsive interactions between dissimilar colloidal particles and attractive interactions between like particles provides a general new route to fabricating self‐organizing bipolar devices. By identifying combinations of conductive device materials between which short‐range repulsive forces exist in the presence of an intervening liquid, electrochemical junctions can be self‐formed, as reported by Chiang and co‐workers on p. 379. The relationship between the performance characteristics of organic field‐effect transistors (OFETs) with 2,5‐bis(4‐biphenylyl)bithiophene/copper hexadecafluorophthalocyanine (BP2T/F₁₆CuPc) heterojunctions and the thickness of the BP2T bottom layer is investigated. Three operating modes (n‐channel, ambipolar, and p‐channel) are obtained by varying the thickness of the organic semiconductor layer. The changes in operating mode are attributable to the morphology of the film and the heterojunction effect, which also leads to an evolution of the field‐effect mobility with increasing film thickness. In BP2T/F₁₆CuPc heterojunctions the mobile charge carriers accumulate at both sides of the heterojunction interface, with an accumulation layer thickness of ca. 10 nm. High field‐effect mobility values can be achieved in continuous and flat films that exhibit the heterojunction effect.