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.     

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.     

Diameter Effect on the Sidewall Functionalization of Single‐Walled Carbon Nanotubes by Addition of Dichlorocarbene

Dichlorocarbene is added to the sidewalls of single‐walled carbon nanotubes (SWNTs) with diameters ranging from 1.2 to 2.2 nm. Small diameter SWNTs are found to react much more easily than large diameter SWNTs. Upon functionalization, the conductance could be largely preserved for almost all SWNTs, while an effective bandgap increase for functionalized metallic SWNTs (m‐SWNTs) and a bandgap reduction for functionalized semiconducting SWNTs (s‐SWNTs) are generally observed. The results suggest that [2 + 1] cycloaddition is an excellent choice of processing, resulting in SWNTs over a large diameter range with electronic properties that are almost unaffected. Furthermore, possible separation of SWNTs according to their diameters could be achieved due to the apparent diameter‐dependent reactivity.     

Reinforcing Epoxy Polymer Composites Through Covalent Integration of Functionalized Nanotubes

Strong interfacial bonding and homogenous dispersion have been found to be necessary conditions to take full advantage of the extraordinary properties of nanotubes for reinforcement of composites. We have developed a fully integrated nanotube composite material through the use of functionalized single‐walled carbon nanotubes (SWNTs). The functionalization was performed via the reaction of terminal diamines with alkylcarboxyl groups attached to the SWNTs in the course of a dicarboxylic acid acyl peroxide treatment. Nanotube‐reinforced epoxy polymer composites were prepared by dissolving the functionalized SWNTs in organic solvent followed by mixing with epoxy resin and curing agent. In this hybrid material system, nanotubes are covalently integrated into the epoxy matrix and become part of the crosslinked structure rather than just a separate component. Results demonstrated dramatic enhancement in the mechanical properties of an epoxy polymer material, for example, 30–70 % increase in ultimate strength and modulus with the addition of only small quantities (1–4 wt.‐%) of functionalized SWNTs. The nanotube‐reinforced epoxy composites also exhibited an increased strain to failure, which suggests higher toughness.     

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.     

Ultrathin Electronic Composite Sheets of Metallic/Semiconducting Carbon Nanotubes Embedded in Conjugated Block Copolymers

Ultrathin composite films consisting of mixtures of metallic (m‐) and semiconducting (s‐) single‐walled carbon nanotubes (SWNTs) with a conjugated block copolymer are developed from a solution‐based process. The electronic properties of the films are precisely controlled from metallic to semiconducting to insulating. The tunability of the electronic composite sheets is mainly attributed to (1) the efficient dispersion of SWNTs with a conjugated block copolymer in solution, (2) the control of the number of nanotubes by centrifugation, and (3) the individually networked deposition of SWNTs embedded in the conjugated block copolymer on the target substrate by spin‐coating. A highly reliable field‐effect transistor with a networked composite film is realized with a specific range of tube density and a high on/off current ratio of approximately 10⁶ which resulted from the Schottky barriers evolved between the individual m‐ and s‐SWNTs in the network. There is also great freedom when choosing both the gate dielectrics and source‐drain electrodes for transistors containing the composite films. Furthermore, the fabricated electronic composites are highly transparent, flexible, and chemically robust and thus, they can be conveniently micropatterned by photolithography, as well as by unconventional transfer printing techniques.     

Polarization‐Sensitive Single‐Wall Carbon Nanotubes All‐in‐One Photodetecting and Emitting Device Working at 1.55 µm

Functional and easy‐to‐integrate nanodevices operating in the telecom wavelength ranges are highly desirable. Indeed, the pursuit for faster, cheaper, and smaller transceivers for datacom applications is fueling the interest in alternative materials to develop the next generation of photonic devices. In this context, single wall carbon nanotubes (SWNTs) have demonstrated outstanding electrical and optical properties that make them an ideal material for the realization of ultracompact optoelectronic devices. Still, the mixture in chirality of as‐synthesized SWNTs and the necessity of precise positioning of SWNT‐based devices hinder the development of practical devices. Here, the realization of operational devices obtained using liquid solution‐based techniques is reported, which allow high‐purity sorting and localized deposition of aligned semiconducting SWNTs (s‐SWNTs). More specifically, devices are demonstrated by combining a polymer assisted extraction method, which enables a very effective selection of s‐SWNTs with a diameter of about 1–1.2 nm, with dielectrophoresis, which localizes the deposition onto silicon wafers in aligned arrays in‐between prepatterned electrodes. Thus, long semiconducting nanotubes directly contact the electrodes and, when asymmetric contacts (i.e., source and drain made of different metals) are used, each device can operate both as photoemitter and as photodetector in the telecom band around 1.55 µm in air at room temperature.     

Carbon Fiber–Bismaleimide Composites Filled with Nickel‐Coated Single‐Walled Carbon Nanotubes for Lightning‐Strike Protection

Multifunctional carbon fiber composites are imperative for next‐generation lightweight aircraft structures. However, lightning‐strike protection is a feature that is lacking in many modern carbon fiber high‐temperature polymer systems, due to their high electrical resistivity. This work presents a study on processing, materials optimization, and property development of high‐temperature bismaleimide (BMI)–carbon fiber composites filled with nickel‐coated single‐walled carbon nanotubes (Ni‐SWNTs) based on three key factors: i) dispersion of Ni‐SWNTs, ii) their surface coverage on the carbon plies and, iii) the composite surface resistivity. Atomic force microscopy analysis revealed that coating purified SWNTs with nickel enabled improved dispersion which resulted in uniform surface coverage on the carbon plies. The electrical resistivity of the baseline composite system was reduced by ten orders of magnitude by the addition of 4 wt% Ni‐SWNTs (calculated with respect to the weight of a single carbon ply). Ni‐SWNT–filled composites showed a reduced amount of damage to simulated lightning strike compared to their unfilled counterparts, as indicated by the minimal carbon fiber pull‐out.     

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.     

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.     

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.     

Individual Dissolution of Single‐Walled Carbon Nanotubes by Using Polybenzimidazole,and Highly Effective Reinforcement of Their Composite Films

Polybenzimidazole (PBI) is shown to individually dissolve/disperse single‐walled carbon nanotubes (SWNTs) in N,N‐dimethylacetamide (DMAc), which is demonstrated by vis‐near IR absorption and photoluminescence spectroscopy and atomic force microscopy observations. By casting these dispersions, SWNTs/PBI composite films were successfully fabricated on substrates without any sign of macroscopic aggregation. The thermal stability and mechanical properties of the composite films were investigated using thermogravimetric analysis (TGA) and tensile tests, respectively, and it was found that, first, the addition of SWNTs to PBI does not deteriorate the thermal stability of the matrix film, and second, the mechanical properties of the PBI film were reinforced by ca. 50% with only 0.06 wt % addition of the SWNTs to the film without reducing the thermal stability of the PBI. Raman spectroscopy of the composite films revealed the existence of an interaction between the PBI and the SWNTs. The individual dissolution of the SWNTs and efficient reinforcement of the PBI are due to the π–π interaction between the PBI and the sidewalls of the SWNTs.     

Reactive Spinning of Cyanate Ester Fibers Reinforced with Aligned Amino‐Functionalized Single Wall Carbon Nanotubes

We report a new approach of reactive spinning to fabricate thermosetting cyanate ester micro‐scale diameter fibers with aligned single walled carbon nanotubes (SWNTs). The composite fibers were produced by first dispersing the SWNTs (1 wt %) in cyanate ester (CE) via solvent blending, followed by pre‐polymerization, spinning and then multiple‐stage curing. The pre‐polymerization, spinning and post‐spinning cure temperatures were carefully controlled to achieve good spun crosslinked fibers. Both pristine and amino‐functionalized SWNTs were used for the reinforced fiber spinning. Amino‐functionalized SWNTs (f‐SWNTs) were prepared by reacting acid‐treated SWNTs with toluene 2,4‐diisocyanate and then ethylenediamine (EDA). FTIR, optical microscopy and scanning electron microscopy (SEM) showed that the amino‐functionalized SWNTs were covalently and uniformly dispersed into the cyanate ester matrix and aligned along the fiber axis. The alignment was further confirmed using polarized Raman spectroscopy. The composite fibers with aligned amino‐functionalized SWNTs possess improved tensile properties with respect to neat CE fibers, showing 85, 140, and 420% increase in tensile strength, elongation and stress‐strain curve area (i.e., toughness), respectively. NH₂‐functionalization of SWNTs improves their dispersibility, alignment and interfacial strength and hence tensile properties of composite spun fibers. Fiber spinning to align SWNTs using thermosetting resin is novel. Others have reported fiber spinning to align SWNTs in thermoplastics. However, thermosetting CE resins offer the advantages of low and controllable viscosity during spinning and reactivity with amino functional groups to enable f‐SWNT/CE covalent bonding.     

碳纳米管非对称接触结构制作及电学性能研究

实验研究了多根或单根单壁碳纳米管与非对称金属电极接触结构的制作方法。先用介电泳方法(DEP)将碳纳米管定向排列在Au电极对之间,再用电子束光刻(EBL)在碳纳米管的一端加工Al电极,获得多根碳纳米管与金铝电极的非对称接触结构。先用EBL在Au电极对一端覆盖Al电极,再用DEP排列碳纳米管,实现单根碳管与金铝电极的非对称接触结构。非对称结构器件的电学测试研究表明,器件的I-V曲线不再对称,呈现出整流特性。     

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.     

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.     

Facile Nondestructive Assembly of Tyrosine‐Rich Peptide Nanofibers as a Biological Glue for Multicomponent‐Based Nanoelectrode Applications

Achieving the nondestructive assembly of carbon nanoelectrodes with multiple components in a scalable manner enables effective electrical interfaces among nanomaterials. Here, a facile nondestructive multiscale assembly of multicomponent nanomaterials using self‐assembled tyrosine‐rich peptide nanofibers (TPFs) as a biological glue is reported. The versatile functionalities of the rationally devised tyrosine‐rich short peptide allow for (1) self‐assembly of the peptide into nanofibers using noncovalent interactions, followed by (2) immobilization of spatially distributed metal nanoparticles on the nanofiber surface, and (3) subsequent assembly with graphitic nanomaterials into a percolated network‐structure. This percolated network‐structure of silver nanoparticle (AgNP)‐decorated peptide nanofibers with imbedded single‐walled carbon nanotubes (SWNTs) proves to be a versatile nanoelectrode platform with excellent processability. The SWNT–TPF–AgNP assembly, when utilized as a flexible and transparent multicomponent electronic film, was quite effective for enhancing direct electron transfer (DET) as verified for a third‐generation glucose sensor composed of this film. The simple solution process used to produce the functional nanomaterials could provide a new platform for scalable manufacturing of novel nanoelectrode materials forming effective electrical contacts with molecules from diverse biological systems.     

Degradable Conjugated Polymers: Synthesis and Applications in Enrichment of Semiconducting Single‐Walled Carbon Nanotubes

Polymers which enrich semiconducting single‐walled carbon nanotubes (SWNTs) and are also removable after enrichment are highly desirable for achieving high‐performance field‐effect transistors (FETs). We have designed and synthesized a new class of alternating copolymers containing main‐chain fluorene and hydrofluoric acid (HF) degradable disilane for sorting and preferentially suspending semiconducting nanotube species. The results of optical absorbance, photoluminescence emission, and resonant Raman scattering show that poly[(9,9‐dioctylfluorenyl‐2,7‐diyl)‐alt‐co‐1,1,2,2‐tetramethyl‐disilane] preferentially suspends semiconducting nanotubes with larger chiral angle (25°–28°) and larger diameter (1.03 nm–1.17 nm) (specifically (8,7), (9,7) and (9,8) species) present in HiPCO nanotube samples. Computer simulation shows that P1 preferentially interacts with (8,7) (semiconducting) over (7,7) (metallic) species, confirming that P1 selects larger diameter, larger chiral angle semiconducting tubes. P1 wrapped on the surface of SWNTs is easily washed off through degradation of the disilane bond of the alternating polymer main chain in HF, yielding “clean” purified SWNTs. We have applied the semiconducting species enriched SWNTs to prepare solution‐processed FET devices with random nanotube network active channels. The devices exhibit stable p‐type semiconductor behavior in air with very promising characteristics. The on/off current ratio reaches up to 15 000, with on‐current level of around 10 μA and estimated hole mobility of 5.2 cm² V^?1 s^?1.     

Bacteriorhodopsin‐Monolayer‐Based Planar Metal–Insulator–Metal Junctions via Biomimetic Vesicle Fusion: Preparation,Characterization, and Bio‐optoelectronic Characteristics

A reliable and reproducible method for preparing bacteriorhodopsin (bR)‐containing metal–biomolecule–monolayer‐metal planar junctions via vesicle fusion tactics and soft deposition of Au top electrodes is reported. Optimum monolayer and junction preparations, including contact effects, are discussed. The electron‐transport characteristics of bR‐containing membranes are studied systematically by incorporating native bR or artificial bR pigments derived from synthetic retinal analogues, into single solid‐supported lipid bilayers. Current–voltage (I–V) measurements at ambient conditions show that a single layer of such bR‐containing artificial lipid bilayers pass current in solid electrode/bilayer/solid electrode structures. The current is passed only if retinal or its analogue is present in the protein. Furthermore, the preparations show photoconductivity as long as the retinal can isomerize following light absorption. Optical characterization suggests that the junction photocurrents might be associated with a photochemically induced M‐like intermediate of bR. I–V measurements along with theoretical estimates reveal that electron transfer through the protein is over four orders of magnitude more efficient than what would be estimated for direct tunneling through 5 nm of water‐free peptides. Our results furthermore suggest that the light‐driven proton‐pumping activity of the sandwiched solid‐state bR monolayer contributes negligibly to the steady‐state light currents that are observed, and that the orientation of bR does not significantly affect the observed I–V characteristics.     

Hexahistidine‐Tagged Single‐Walled Carbon Nanotubes (His6‐tagSWNTs): A Multifunctional Hard Template for Hierarchical Directed Self‐Assembly and Nanocomposite Construction

While a hexahistidine affinity tag can be introduced at protein termini or internal sites by standard molecular biology procedures for purification, immobilization, or labeling of proteins, here the versatility of this concept is exploited for the chemical preparation of novel hexahistidine‐tagged single‐walled carbon nanotubes (His₆‐tagSWNTs), a novel hard template useful for solubilizing, assembling, processing, and interfacing SWNTs in aqueous conditions. Water‐soluble and exfoliated His₆‐tagSWNTs are prepared and fully characterized. This functional molecular module is able to interact via robust physisorption (π?π stacking) with the sidewall of SWNTs and combines the versatility of small, water‐soluble reporters (His₆) for hierarchical directed self‐assembly (HDSA) and construction of nanocomposites. It is demonstrated that metal coordination bonds with Ni(II) can be used for the supramolecular self assembly of His₆‐tagSWNTs, generating complex reticulated networks and architectures. The His₆‐tagSWNTs hard template nanohybrid is further utilized for directed self‐assembly with silica nanoparticles. The versatility of the novel hybrids opens a new era for the rational design, smart (bio)functionalization, processing, interfacing, and self assembling of carbon nanotubes for the construction of multicomposites and more complex systems with controllable spatial organization and programmable properties for a wide range of applications in biology, nanoelectronics, and catalysis.