Clay Assisted Dispersion of Carbon Nanotubes in Conductive Epoxy Nanocomposites

Clay was introduced into single‐walled carbon nanotube (SWNT)/epoxy composites to improve nanotube dispersion without harming electrical conductivity or mechanical performance. Unlike surfactant or polymer dispersants, clay is mechanically rigid and known to enhance the properties (e.g., modulus, gas barrier, and flame retardation) of polymer composites. Combining nanotubes and clay allows both electrical and mechanical behavior to be simultaneously enhanced. With just 0.05 wt % SWNT, electrical conductivity is increased by more than four orders of magnitude (from 10^–9 to 10^–5 S cm^–1) with the addition of 0.2 wt % clay. Furthermore, the percolation threshold of these nanocomposites is reduced from 0.05 wt % SWNT to 0.01 wt % with the addition of clay. SWNTs appear to have an affinity for clay that causes them to become more exfoliated and better networked in these composites. This clay‐nanotube synergy may make these composites better suited for a variety of packaging, sensing, and shielding applications.     

Effect of Nanotube Functionalization on the Coefficient of Thermal Expansion of Nanocomposites

Single‐walled carbon nanotubes (SWNTs) are functionalized through both covalent and noncovalent bonding approaches to enhance dispersion and interfacial bonding. The coefficient of thermal expansion (CTE) of the functionalized‐SWNT‐reinforced epoxy composites are measured with a thermal mechanical analyzer (TMA). Experimental results indicate that changes of the glass‐transition temperature (T_g) in functionalized SWNT–polymer composites are dependent upon the functionalization methods. The CTE below the glass‐transition temperature of nanocomposites with a 1 wt % loading of nanotubes is substantially diminished compared to a neat polymer. A reduction in the CTE of up to 52 % is observed for nanocomposites using functionalized nanotubes. However, the CTE above the T_g significantly increases because of the contribution from phonon mode and Brownian motions of a large number of SWNTs in resin‐crosslinked networks, but the increments are compromised by possible interfacial confinement. A tunable CTE induced through nanotube functionalization has application potentials for high‐performance composites, intelligent materials, and circuit protections.     

Direct visualization of percolation paths in carbon nanotube/polymer composites

Composites of single-walled carbon nanotubes (SWNT) and conjugated polymers are highly interesting as active semiconducting layers in solution-processable and flexible electronics. Understanding the percolation behavior and percolation threshold for electrical conductivity in these composites is a prerequisite for future applications. Here, we investigate the concentration and length dependence of on-currents and apparent mobilities for selectively dispersed, semiconducting (6,5) single-walled carbon nanotubes in a matrix of the dispersing polyfluorene-bipyridine copolymer (PFO-BPy) through field-effect transistor measurements. More importantly, we directly visualize the percolation paths at and above the percolation limit by near-infrared electroluminescence (EL) imaging with high spatial resolution. EL imaging reveals the various shapes of critical percolation paths at the threshold and the non-uniformity of charge transport even at high SWNT concentrations. We also find that percolation paths differ depending on the assignment of the injecting electrodes probably due to different injection barriers and variation of nanotube density at the electrodes.     

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.     

A Versatile,Molecular Engineering Approach to Simultaneously Enhanced,Multifunctional Carbon‐Nanotube– Polymer Composites

Single‐walled carbon nanotubes (SWNTs) are recognized as the ultimate carbon fibers for high‐performance, multifunctional composites. The remarkable multifunctional properties of pristine SWNTs have proven, however, difficult to harness simultaneously in polymer composites, a problem that arises largely because of the smooth surface of the carbon nanotubes (i.e., sidewalls), which is incompatible with most solvents and polymers, and leads to a poor dispersion of SWNTs in polymer matrices, and weak SWNT–polymer adhesion. Although covalently functionalized carbon nanotubes are excellent reinforcements for mechanically strong composites, they are usually less attractive fillers for multifunctional composites, because the covalent functionalization of nanotube sidewalls can considerably alter, or even destroy, the nanotubes' desirable intrinsic properties. We report for the first time that the molecular engineering of the interface between non‐covalently functionalized SWNTs and the surrounding polymer matrix is crucial for achieving the dramatic and simultaneous enhancement in mechanical and electrical properties of SWNT–polymer composites. We demonstrate that the molecularly designed interface of SWNT–matrix polymer leads to multifunctional SWNT–polymer composite films stronger than pure aluminum, but with only half the density of aluminum, while concurrently providing electroconductivity and room‐temperature solution processability.     

Photosensitive Carbon Nanotube Paste Based on Acrylated Single‐Walled Carbon Nanotubes

A novel photosensitive carbon nanotube (CNT) paste based on an acrylated single‐walled carbon nanotube (ac‐SWNT), a cross‐linking agent, and a photoinitiator has been prepared. Unlike the conventional photosensitive CNT pastes reported to date, our photosensitive paste system does not use a polymeric binder for the photopolymerization following UV exposure because the ac‐SWNT itself has cross‐linkable groups. Therefore, the subsequent firing process can be performed at relatively low temperatures and the residue of the organic vehicle in the SWNT pattern is minimized after firing. The ac‐SWNT was synthesized from the reaction between carboxylated SWNT (ca‐SWNT) and methacryloyl chloride in the presence of base, and its structure was characterized by Fourier transform infrared, Raman, and X‐ray photoelectron spectroscopy. After UV exposure and development with N,N‐dimethyl formamide a pattern with a resolution of 8 µm was obtained from the photosensitive CNT paste, which was then fired at 300 °C to give a clear SWNT pattern. When the photosensitive CNT paste was used for the fabrication of a cathode emitter for field emission displays, the CNT pattern emitted electrons under an applied electrical field with emission characteristics comparable with those obtained with screen‐printing from conventional CNT pastes. Therefore, such a photosensitive paste for fabricating SWNT patterns can be used in the production of field‐emission displays and in future device integration requiring carbon nanotubes, because it provides large‐area patterning of SWNT with high stability and uniformity.     

Dispersion State and Fiber Toughness: Antibacterial Lysozyme‐Single Walled Carbon Nanotubes

Novel multicomponent fibers that include single‐walled carbon nanotubes (SWNT) and lysozyme (LSZ) are reported. These fibers exhibit antibacterial and mechanical properties suitable for fabrics, clothing and technical textiles in medical environments. The challenging combination of several components in a single fiber material is achieved via fundamental studies on the phase behavior of aqueous LSZ–SWNT dispersions. The addition of molecular cationic surfactants proved to be critical to achieving stable liquid mixtures that can be spun into fibers. In the absence of the cationic surfactant tetradecyl trimethylammonium bromide (TTAB), depletion effects result in large aggregates at relatively low SWNT concentration. However, the addition of TTAB increases the concentration at which demixing occurrs by approximately one order of magnitude. Dry‐spun fibers with significant antibacterial activity and toughness are obtained from LSZ–TTAB–SWNT dispersions combined with a polyvinyl alcohol (PVA) solution. Toughness is strongly affected by the initial dispersion state. The most remarkable fibers are produced from concentrated LSZ–TTAB–SWNT supernatants; they both have four times the toughness of spider silk and 70% of the native LSZ activity.     

Protamine Functionalized Single‐Walled Carbon Nanotubes for Stem Cell Labeling and In Vivo Raman/Magnetic Resonance/Photoacoustic Triple‐Modal Imaging

Stem cells have shown great potential in regenerative medicine and attracted tremendous interests in recent years. Sensitive and reliable methods for stem cell labeling and in vivo tracking are thus urgently needed. Here, a novel approach to label human mesenchymal stem cells (hMSCs) with single‐walled carbon nanotubes (SWNTs) for in vivo tracking by triple‐modal imaging is presented. It is shown that polyethylene glycol (PEG) functionalized SWNTs conjugated with protamine (SWNT‐PEG‐PRO) exhibit extremely efficient cell entry into hMSCs, without affecting their proliferation and differentiation. The strong inherent resonance Raman scattering of SWNTs is used for in vitro and in vivo Raman imaging of SWNT‐PEG‐PRO‐labeled hMSCs, enabling ultrasensitive in vivo detection of as few as 500 stem cells administrated into mice. On the other hand, the metallic catalyst nanoparticles attached on nanotubes can be utilized as the T2‐contrast agent in magnetic resonance (MR) imaging of SWNT‐labeled hMSCs. Moreover, in vivo photoacoustic imaging of hMSCs in mice is also demonstrated. The work reveals that SWNTs with appropriate surface functionalization have the potential to serve as multifunctional nanoprobes for stem cell labeling and multi‐modal in vivo tracking.     

Electrical Conductivity of Film Composites Based on Polyvinyledene Fluoride with Carbon Nanotubes

The results of a study of film composites based on polyvinylidene fluoride with carbon nanotubes (CNTs) by dielectric relaxation spectroscopy are presented. For composite samples containing more than 0.5 wt % of nanotubes, nonlinear current–voltage characteristics are obtained. The concentration dependences of the electrical conductivity of the composites are examined and the percolation threshold for the samples under study is determined. It is shown that an insignificant increase in the electrical conductivity of the composites is observed even upon filling with 0.2 wt % of CNTs, whereas the electrical conductivity becomes three orders of magnitude higher upon the introduction of 1 wt% of CNTs and is seven orders of magnitude higher at more than 3 wt %, compared with the unfilled polymer. This confirms that CNTs are promising for the development of electrically conducting composites and film materials on the basis of polyvinylidene fluoride.     

Electrical Power From Nanotube and Graphene Electrochemical Thermal Energy Harvesters

Nanocarbon‐based thermocells involving aqueous potassium ferro/ferricyanide electrolyte are investigated as an alternative to conventional thermoelectrics for thermal energy harvesting. The dependencies of power output on thermocell parameters, such as cell orientation, electrode size, electrode spacing, electrolyte concentration and temperature, are examined to provide practical design elements and principles. Observation of thermocell discharge behavior provides an understanding of the three primary internal resistances (i.e., activation, ohmic and mass transport overpotentials). The power output from nanocarbon thermocells is found to be mainly limited by the ohmic resistance of the electrolyte and restrictions on mass transport in the porous nanocarbon electrode due to pore tortuosity. Based on these fundamental studies, a comparison of power generation is conducted using various nanocarbon electrodes, including purified single‐walled and multi‐walled carbon nanotubes (P‐SWNTs and P‐MWNTs, respectively), unpurified SWNTs, reduced graphene oxide (RGO) and P‐SWNT/RGO composite. The P‐SWNT thermocell has the highest specific power generation per electrode weight (6.8 W/kg for a temperature difference of 20 °C), which is comparable to that for the P‐MWNT electrode. The RGO thermocell electrode provides a substantially lower specific power generation (3.9 W/kg).     

Control of Current Hysteresis of Networked Single‐Walled Carbon Nanotube Transistors by a Ferroelectric Polymer Gate Insulator

Films made of 2D networks of single‐walled carbon nanotubes (SWNTs) are one of the most promising active‐channel materials for field‐effect transistors (FETs) and have a variety of flexible electronic applications, ranging from biological and chemical sensors to high‐speed switching devices. Challenges, however, still remain due to the current hysteresis of SWNT‐containing FETs, which has hindered further development. A new and robust method to control the current hysteresis of a SWNT‐network FET is presented, which involves the non‐volatile polarization of a ferroelectric poly(vinylidene fluoride‐trifluoroethylene) (P(VDF‐TrFE)) gate insulator. A top‐gate FET with a solution‐processed SWNT‐network exhibits significant suppression of the hysteresis when the gate‐voltage sweep is greater than the coercive field of the ferroelectric polymer layer (≈50 MV m^?1). These near‐hysteresis‐free characteristics are believed to be due to the characteristic hysteresis of the P(VDF‐TrFE), resulting from its non‐volatile polarization, which makes effective compensation for the current hysteresis of the SWNT‐network FETs. The onset voltage for hysteresis‐minimized operation is able to be tuned simply by controlling the thickness of the ferroelectric film, which opens the possibility of operating hysteresis‐free devices with gate voltages down to a few volts.     

Hierarchical Inorganic–Organic Nanocomposites Possessing Amphiphilic and Morphological Complexities: Influence of Nanofiller Dispersion on Mechanical Performance

Novel nanocomposites possessing ternary compositions and complex morphologies have been prepared from amphiphilic crosslinked hyperbranched fluoropolymer–poly(ethylene glycol) (HBFP–PEG) in the presence of pristine and chemically functionalized nanoscopic fillers, single‐walled carbon nanotubes (SWNTs) and silica nanoparticles (SiO₂). Both SWNTs and SiO₂ were engineered specifically to become phase‐designated reinforcing functional materials, SWNT‐g‐PEG and SiO₂‐g‐HBFP, which (1) improved the dispersion of fillers, nanotubes, or spherical nanoparticles in the amphiphilic matrices, (2) enhanced the non‐covalent interactions between nanofillers and polymers, and more importantly, (3) maintained reactive functionalities to be further covalently integrated into the complex networks. Tensile moduli (E_dry) for these as‐prepared SWNT‐containing composites increased by up to 430% relative to the unfilled material, while those incorporated with SiO₂ had a 420% increase of E_dry. After swelling in water, the water absorption within the micro‐ and nanochannels of PEG‐rich domains rigidified or softened the entire crosslinked network, as determined by the amount of PEG.     

Morphological and Chemical/Physical Characterization of Fe‐Doped Synthetic Chrysotile Nanotubes

In the field of thin‐layer‐structured inorganic nanotubes, morphological, structural, and chemical/physical modifications induced in synthetic stoichiometric chrysotile nanotubes have been evaluated as a function of the extent of Fe doping. Fe‐doped synthetic chrysotile nanocrystals have been obtained in the range from 0.29 wt.‐% up to 1.37 wt.‐% Fe. A partial Fe replacement for Si and Mg has been observed through the modification of Fourier‐transform infrared (FTIR) absorption bands. FTIR spectroscopic, X‐ray diffraction, and thermogravimetric analyses provide evidence for Fe inclusion into the chrysotile crystal structure, in both octahedral and tetrahedral sites, which induces a flattening of the curved brucite‐like layers in the stoichiometric chrysotile. Further characterization by morphological analysis (scanning electron microscopy, transmission electron microscopy, and atomic force microscopy) has revealed the effect of Fe doping on the aggregation of chrysotile nanotubes. The results appear interesting in light of the proposed possibilities of synthetic chrysotile fibers to represent an alternative to carbon nanotubes for innovative technological applications.     

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.     

Effect of SWNT Defects on the Electron Transfer Properties in P3HT/SWNT Hybrid Materials

Poly(3‐hexylthiophene) (P3HT) hybrids with single‐walled carbon nanotubes (SWNTs) were prepared using a series of SWNTs with various defect contents on their surfaces. The hybrids were synthesized by exploiting the π–π interaction between P3HT and the SWNTs, resulting in efficient dispersion of the carbon nanotubes in the P3HT solution. UV‐visible and photoluminescence (PL) spectra showed that the carbon nanotubes quench the PL of P3HT in the hybrids, indicating that electron transfer occurs from photo‐excited P3HT to the SWNTs. This electron transfer from P3HT to carbon nanotubes was disrupted by the presence of defects on the SWNT surfaces. However, the PL lifetime of P3HT in the hybrids was found to be the same as that of pure P3HT in solution, indicating the formation of a ground‐state non‐fluorescent complex of P3HT/SWNTs.     

Bilayer Organic–Inorganic Gate Dielectrics for High‐Performance,Low‐Voltage,Single‐Walled Carbon Nanotube Thin‐Film Transistors,Complementary Logic Gates,and p–n Diodes on Plastic Substrates

High‐capacitance bilayer dielectrics based on atomic‐layer‐deposited HfO₂ and spin‐cast epoxy are used with networks of single‐walled carbon nanotubes (SWNTs) to enable low‐voltage, hysteresis‐free, and high‐performance thin‐film transistors (TFTs) on silicon and flexible plastic substrates. These HfO₂–epoxy dielectrics exhibit excellent properties including mechanical flexibility, large capacitance (up to ca. 330 nF cm^–2), and low leakage current (ca. 10^–8 A cm^–2); their low‐temperature (ca. 150 °C) deposition makes them compatible with a range of plastic substrates. Analysis and measurements of these dielectrics as gate insulators in SWNT TFTs illustrate several attractive characteristics for this application. Their compatibility with polymers used for charge‐transfer doping of SWNTs is also demonstrated through the fabrication of n‐channel SWNT TFTs, low‐voltage p–n diodes, and complementary logic gates.     

A Facile Strategy for Preparation of Fluorescent SWNT Complexes with High Quantum Yields Based on Ion Exchange

The fluorescent imidazolium salt (1,3‐bis(9‐anthracenylmethyl)imidazolium chloride, [bamim]Cl) has been grafted onto the surfaces of single‐walled carbon nanotubes (SWNTs) using an ion exchange strategy based on metathesis of the K⁺ ion in CO₂K derivatized SWNTs with [bamim]⁺. The resulting SWNT‐[bamim] complex has been characterized with high‐resolution transmission electron microscopy (HR‐TEM), X‐ray photoelectron spectroscopy (XPS), elemental mapping, and elemental linear profiles analysis. A blue light emission can be observed at 392, 414 and 438 nm for SWNT‐[bamim] upon being excited at 254 nm. The quantum yield (QY) of the SWNT‐[bamim] complex (0.40) is much higher than that of SWNT/[bamim]Cl (0.02), used as a control, and prepared using a π‐π stacking method, indicating that ion exchange is a far more effective strategy for retaining a high QY. Additionally, UV‐Vis‐NIR and Raman spectroscopy show that the SWNT‐[bamim] complex can maintain the one‐dimensional electronic states of SWNTs. Other imidazolium salts have also been successfully grafted onto SWNTs via the same strategy, indicating that the ion exchange process can serve as a universal strategy for the functionalization of SWNTs.     

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.     

Cover Picture: Bilayer Organic–Inorganic Gate Dielectrics for High‐Performance,Low‐Voltage,Single‐Walled Carbon Nanotube Thin‐Film Transistors,Complementary Logic Gates,and p–n Diodes on Plastic Substrates (Adv. Funct. Mater. 18/2006)

Low‐voltage, hysteresis‐free, flexible thin‐film‐type electronic systems based on networks of single‐walled carbon nanotubes and bilayer organic–inorganic nanodielectrics are detailed in work by Rogers and co‐workers reported on p. 2355. The cover image shows a schematic array of such thin‐film transistors (TFTs) on a plastic substrate. The structure of the bilayer nanodielectric, which consists of a film of HfO₂ formed by atomic layer deposition and an ultrathin layer of epoxy formed by spin‐casting, is also illustrated schematically. High‐capacitance bilayer dielectrics based on atomic‐layer‐deposited HfO₂ and spin‐cast epoxy are used with networks of single‐walled carbon nanotubes (SWNTs) to enable low‐voltage, hysteresis‐free, and high‐performance thin‐film transistors (TFTs) on silicon and flexible plastic substrates. These HfO₂–epoxy dielectrics exhibit excellent properties including mechanical flexibility, large capacitance (up to ca. 330 nF cm^–2), and low leakage current (ca. 10^–8 A cm^–2); their low‐temperature (ca. 150 °C) deposition makes them compatible with a range of plastic substrates. Analysis and measurements of these dielectrics as gate insulators in SWNT TFTs illustrate several attractive characteristics for this application. Their compatibility with polymers used for charge‐transfer doping of SWNTs is also demonstrated through the fabrication of n‐channel SWNT TFTs, low‐voltage p–n diodes, and complementary logic gates.     

Synthesis and Properties of a Water‐Soluble Single‐Walled Carbon Nanotube–Poly(m‐aminobenzene sulfonic acid) Graft Copolymer

Poly(m‐aminobenzene sulfonic acid) (PABS), was covalently bonded to single‐walled carbon nanotubes (SWNTs) to form a water‐soluble nanotube–polymer compound (SWNT–PABS). The conductivity of the SWNT–PABS graft copolymer was about 5.6 × 10^–3 S cm^–1, which is much higher than that of neat PABS (5.4 × 10^–7 S cm^–1). The mid‐IR spectrum confirmed the formation of an amide bond between the SWNTs and PABS. The ¹H NMR spectrum of SWNT–PABS showed the absence of free PABS, while the UV/VIS/NIR spectrum of SWNT–PABS showed the presence of the interband transitions of the semiconducting SWNTs and an absorption at 17 750 cm^–1 due to the PABS addend.