Selective Breakdown of Metallic Pathways in Double‐Walled Carbon Nanotube Networks

Covalently functionalized, semiconducting double‐walled carbon nanotubes exhibit remarkable properties and can outperform their single‐walled carbon nanotube counterparts. In order to harness their potential for electronic applications, metallic double‐walled carbon nanotubes must be separated from the semiconductors. However, the inner wall is inaccessible to current separation techniques which rely on the surface properties. Here, the first approach to address this challenge through electrical breakdown of metallic double‐walled carbon nanotubes, both inner and outer walls, within networks of mixed electronic types is described. The intact semiconductors demonstrate a ～62% retention of the ON‐state conductance in thin film transistors in response to covalent functionalization. The selective elimination of the metallic pathways improves the ON/OFF ratio, by more than 360 times, to as high as 40 700, while simultaneously retaining high ON‐state conductance.     

Single functional group interactions with individual carbon nanotubes

Carbon nanotubes display a consummate blend of materials properties that affect applications ranging from nanoelectronic circuits and biosensors to field emitters and membranes. These applications use the non-covalent interactions between the nanotubes and chemical functionalities, often involving a few molecules at a time. Despite their wide use, we still lack a fundamental understanding and molecular-level control of these interactions. We have used chemical force microscopy to measure the strength of the interactions of single chemical functional groups with the sidewalls of vapour-grown individual single-walled carbon nanotubes. Surprisingly, the interaction strength does not follow conventional trends of increasing polarity or hydrophobicity, and instead reflects the complex electronic interactions between the nanotube and the functional group. Ab initio calculations confirm the observed trends and predict binding force distributions for a single molecular contact that match the experimental results. Our analysis also reveals the important role of molecular linkage dynamics in determining interaction strength at the single functional group level.     

Diameter‐ and Metallicity‐Selective Enrichment of Single‐Walled Carbon Nanotubes Using Polymethacrylates with Pendant Aromatic Functional Groups

Current methods for the synthesis of single‐walled nanotubes (SWNTs) produce mixtures of semiconducting (sem‐) and metallic (met‐) nanotubes. Most approaches to the chemical separation of sem‐/met‐SWNTs are based on small neutral molecules or conjugated aromatic polymers, which characteristically have low separation/dispersion efficiencies or present difficulties in the postseparation removal of the polymer so that the resulting field‐effect transistors (FETs) have poor performance. In this Full Paper, the use of three polymethacrylates with different pendant aromatic functional groups to separate cobalt–molybdenum catalyst (CoMoCAT) SWNTs according to their metallicity and diameters is reported. UV/Vis/NIR spectroscopy indicates that poly(methyl‐methacrylate‐co‐fluorescein‐o‐acrylate) (PMMAFA) and poly(9‐anthracenylmethyl‐methacrylate) (PAMMA) preferentially disperse semiconducting SWNTs while poly(2‐naphthylmethacrylate) (PNMA) preferentially disperses metallic SWNTs, all in dimethylforamide (DMF). Photoluminescence excitation (PLE) spectroscopy indicates that all three polymers preferentially disperse smaller‐diameter SWNTs, particularly those of (6,5) chirality, in DMF. When chloroform is used instead of DMF, the larger‐diameter SWNTs (8,4) and (7,6) are instead selected by PNMA. The solvent effects suggest that diameter selectivity and change of polymer conformation is probably responsible. Change of the polymer fluorescence upon interaction with SWNTs indicates that metallicity selectivity presumably results from the photon‐induced dipole–dipole interaction between polymeric chromophore and SWNTs. Thin‐film FET devices using semiconductor‐enriched solution with PMMAFA have been successfully fabricated and the device performance confirms the sem‐SWNTs enrichment with a highly reproducible on/off ratio of about 10³.     

Electronic Property Modification of Single‐Walled Carbon Nanotubes by Encapsulation of Sulfur‐Terminated Graphene Nanoribbons

The use of carbon nanotubes (CNTs) as cylindrical reactor vessels has become a viable means for synthesizing graphene nanoribbons (GNRs). While previous studies demonstrated that the size and edge structure of the as‐produced GNRs are strongly dependent on the diameter of the tubes and the nature of the precursor, the atomic interactions between GNRs and surrounding CNTs and their effect on the electronic properties of the overall system are not well understood. Here, it is shown that the functional terminations of the GNR edges can have a strong influence on the electronic structure of the system. Analysis of SWCNTs before and after the insertion of sulfur‐terminated GNRs suggests a metallization of the majority of semiconducting SWCNTs. This is indicated by changes in the radial breathing modes and the D and G band Raman features, as well as UV–vis–NIR absorption spectra. The variation in resonance conditions of the nanotubes following GNR insertion make direct (n,m) assignment by Raman spectroscopy difficult. Thus, density functional theory calculations of representative GNR/SWCNT systems are performed. The results confirm significant changes in the band structure, including the development of a metallic state in the semiconducting SWCNTs due to sulfur/tube interactions. The GNR‐induced metallization of semiconducting SWCNTs may offer a means of controlling the electronic properties of bulk CNT samples and eliminate the need for a physical separation of semiconducting and metallic tubes.     

Hierarchical Hydrogen Bonds Directed Multi‐Functional Carbon Nanotube‐Based Supramolecular Hydrogels

Supramolecular hydrogels (SMHs) are three‐dimensional networks filled with a large amount of water. The crosslinking force in the 3D network is always constructed by relatively weak and dynamic non‐covalent interactions, and thus SMHs usually possess extremely high susceptibility to external environment and can show extraordinary stimuli‐responsive, self‐healing or other attractive properties. However, the overall crosslinking force in hydrogel networks is difficult to flexibly modulate, and this leads to limited functions of the SMHs. In this regard, hierarchical hydrogen bonds, that is, the mixture of relatively strong and relatively weak hydrogen bonds, are used herein as crosslinking force for the hydrogel preparation. The ratio of strong and weak hydrogen bonds can be finely tuned to tailor the properties of resultant gels. Thus, by delicate manipulation of the overall crosslinking force in the system, a hydrogel with multiple (thermal, pH and NIR light) responsiveness, autonomous self‐healing property and interesting temperature dependent, reversible adhesion behavior is obtained. This kind of hierarchical hydrogen bond manipulation is proved to be a general method for multiple‐functionality hydrogel preparation, and the resultant material shows potential for a range of applications.     

Mechanical Peeling of Free‐Standing Single‐Walled Carbon‐Nanotube Bundles

An in situ electron microscopy study is presented of adhesion interactions between single‐walled carbon nanotubes (SWNTs) by mechanically peeling thin free‐standing SWNT bundles using in situ nanomanipulation techniques inside a high‐resolution scanning electron microscope. The in situ measurements clearly reveal the process of delaminating one SWNT bundle from its originally bound SWNT bundle in a controlled‐displacement manner and capture the deformation curvature of the delaminated SWNT bundle during the peeling process. A theoretical model based on nonlinear elastica theory is employed to interpret the measured deformation curvatures of the SWNTs and to quantitatively evaluate the peeling force and the adhesion strength between bundled SWNTs. The estimated adhesion energy per unit length for each pair of neighboring tubes in the peeling interface based on our peeling experiments agrees reasonably well with the theoretical value. This in situ peeling technique provides a potential new method for separating bundled SWNTs without compromising their material properties. The combined peeling experiments and modeling presented in this paper will be very useful to the study of the adhesion interactions between SWNTs and their nonlinear mechanical behaviors in the large‐displacement regime.     

Carbon Nanotube‐Quantum Dot Nanohybrids: Coupling with Single‐Particle Control in Aqueous Solution

A strategy is reported for the controlled assembly of organic‐inorganic heterostructures consisting of individual single‐walled carbon nanotubes (SWCNTs) selectively coupled to single semiconductor quantum dots (QDs). The assembly in aqueous solution was controlled towards the formation of monofunctionalized SWCNT‐QD structures. Photoluminescence studies in solution, and on surfaces at the single nanohybrid level, showed evidence of electronic coupling between the two nanostructures. The ability to covalently couple heterostructures with single particle control is crucial for the design of novel QD‐based optoelectronic and light‐energy conversion devices.     

Routes towards separating metallic and semiconducting nanotubes

Separation of single-walled carbon nanotubes (SWNTs), according to their electronic characteristics, is essential to the development of molecular electronics, including field-effect transistors. Recent efforts by many groups have used non-covalent and covalent sidewall chemistry to probe differential reactivity in metallic and semiconducting nanotubes. These chemically based methods may more easily effect the bulk separation of tubes, as compared with physical techniques associated with (i) alternating current dielectrophoresis as well as (ii) the current-induced oxidation of metallic nanotubes, that have recently been reported as alternative methods of achieving chiral separations of nanotubes. Exploration of these types of reactions is critical for the development of interesting chemical and physical properties at the interface between molecules and materials as well as for establishing protocols for the selective functionalization of nanotubes.     

Assembly and Electronic Applications of Colloidal Nanomaterials

Artificial solids and thin films assembled from colloidal nanomaterials give rise to versatile properties that can be exploited in a range of technologies. In particular, solution‐based processes allow for the large‐scale and low‐cost production of nanoelectronics on rigid or mechanically flexible substrates. To achieve this goal, several processing steps require careful consideration, including nanomaterial synthesis or exfoliation, purification, separation, assembly, hybrid integration, and device testing. Using a ubiquitous electronic device – the field‐effect transistor – as a platform, colloidal nanomaterials in three electronic material categories are reviewed systematically: semiconductors, conductors, and dielectrics. The resulting comparative analysis reveals promising opportunities and remaining challenges for colloidal nanomaterials in electronic applications, thereby providing a roadmap for future research and development.     

Polyarene‐Functionalized Fullerenes in Carbon Nanotubes: Towards Controlled Geometry of Molecular Chains

Mechanisms for controlling the assembly of molecular arrays in carbon nanotubes via alteration of the size and geometry of the functional groups attached to the molecules inserted into the nanotubes are studied. As model compounds, a series of structurally related fullerenes functionalized with polyaryl groups (C₆₀X, where X is a polyaryl group) of various lengths are synthesized to explore this effect. These molecules are inserted into single‐walled carbon nanotubes (SWNTs) under mild conditions to prevent their decomposition and to form C₆₀X@SNWT structures. The molecular chains thus formed are studied by high‐resolution transmission electron microscopy, X‐ray diffraction, and Raman spectroscopy, revealing that the functional groups increase the interfullerene separation proportionally with the size of X. However, the functional groups themselves appear to adopt various orientations with respect to each other and exhibit intermolecular π–π interactions within the cavities of the carbon nanotubes. All these effects create a distribution of observed interfullerene separations in nanotubes, which are examined by theoretical simulations and interpreted in terms of molecular geometries and intermolecular interactions.     

Double‐Walled Carbon Nanotube Processing

Single‐walled carbon nanotubes (SWCNTs) have been the focus of intense research, and the body of literature continues to grow exponentially, despite more than two decades having passed since the first reports. As well as extensive studies of the fundamental properties, this has seen SWCNTs used in a plethora of applications as far ranging as microelectronics, energy storage, solar cells, and sensors, to cancer treatment, drug delivery, and neuronal interfaces. On the other hand, the properties and applications of double‐walled carbon nanotubes (DWCNTs) have remained relatively under‐explored. This is despite DWCNTs not only sharing many of the same unique characteristics of their single‐walled counterparts, but also possessing an additional suite of potentially advantageous properties arising due to the presence of the second wall and the often complex inter‐wall interactions that arise. For example, it is envisaged that the outer wall can be selectively functionalized whilst still leaving the inner wall in its pristine state and available for signal transduction. A similar situation arises in DWCNT field effect transistors (FETs), where the outer wall can provide a convenient degree of chemical shielding of the inner wall from the external environment, allowing the excellent transconductance properties of the pristine nanotubes to be more fully exploited. Additionally, DWCNTs should also offer unique opportunities to further the fundamental understanding of the inter‐wall interactions within and between carbon nanotubes. However, the realization of these goals has so far been limited by the same challenge experienced by the SWCNT field until recent years, namely, the inherent heterogeneity of raw, as‐produced DWCNT material. As such, there is now an emerging field of research regarding DWCNT processing that focuses on the preparation of material of defined length, diameter and electronic type, and which is rapidly building upon the experience gained by the broader SWCNT community. This review describes the background of the field, summarizing some relevant theory and the available synthesis and purification routes; then provides a thorough synopsis of the current state‐of‐the‐art in DWCNT sorting methodologies, outlines contemporary challenges in the field, and discusses the outlook for various potential applications of the resulting material.     

Terpyridine-functionalized surfaces: redox-active, switchable, and electroactive nanoarchitecturesgland

Terpyridines represent versatile functional supramolecular building blocks that are easily integrated in numerous devices and can readily modify surfaces. In particular, redox-active complexes with terpyridine ligands have been attached to surfaces, either by covalent or non-covalent interactions, and form highly ordered mono- or multilayer systems, since electronic and charge transport properties are major topics of interest. Their applications in nanoelectronics are a driving force for understanding and enabling the utilization of the supramolecular properties of terpyridines for surface modification. This area of research has received increasing attention during the last decade leading into the supramacromolecular regime. This Progress Report presents an overview of the state-of-the-art of surface modifications utilizing terpyridine systems and highlights main results, as well as modern trends, in this research area.     

High‐Performance Partially Aligned Semiconductive Single‐Walled Carbon Nanotube Transistors Achieved with a Parallel Technique

Single‐walled carbon nanotubes (SWNTs) are widely thought to be a strong contender for next‐generation printed electronic transistor materials. However, large‐scale solution‐based parallel assembly of SWNTs to obtain high‐performance transistor devices is challenging. SWNTs have anisotropic properties and, although partial alignment of the nanotubes has been theoretically predicted to achieve optimum transistor device performance, thus far no parallel solution‐based technique can achieve this. Herein a novel solution‐based technique, the immersion‐cum‐shake method, is reported to achieve partially aligned SWNT networks using semiconductive (99% enriched) SWNTs (s‐SWNTs). By immersing an aminosilane‐treated wafer into a solution of nanotubes placed on a rotary shaker, the repetitive flow of the nanotube solution over the wafer surface during the deposition process orients the nanotubes toward the fluid flow direction. By adjusting the nanotube concentration in the solution, the nanotube density of the partially aligned network can be controlled; linear densities ranging from 5 to 45 SWNTs/μm are observed. Through control of the linear SWNT density and channel length, the optimum SWNT‐based field‐effect transistor devices achieve outstanding performance metrics (with an on/off ratio of ~3.2 × 10⁴ and mobility 46.5 cm²/Vs). Atomic force microscopy shows that the partial alignment is uniform over an area of 20 × 20 mm² and confirms that the orientation of the nanotubes is mostly along the fluid flow direction, with a narrow orientation scatter characterized by a full width at half maximum (FWHM) of <15° for all but the densest film, which is 35°. This parallel process is large‐scale applicable and exploits the anisotropic properties of the SWNTs, presenting a viable path forward for industrial adoption of SWNTs in printed, flexible, and large‐area electronics.     

Thread‐like Supercapacitors Based on One‐Step Spun Nanocomposite Yarns

Thread‐like electronic devices have attracted great interest because of their potential applications in wearable electronics. To produce high‐performance, thread‐like supercapacitors, a mixture of stable dispersions of single‐walled carbon nanotubes and conducting polyaniline nanowires are prepared. Then, the mixture is spun into flexible yarns with a polyvinyl alcohol outer sheath by a one‐step spinning process. The composite yarns show excellent mechanical properties and high electrical conductivities after sufficient washing to remove surfactants. After applying a further coating layer of gel electrolyte, two flexible yarns are twisted together to form a thread‐like supercapacitor. The supercapacitor based on these two yarns (SWCNTs and PAniNWs) possesses a much higher specific capacitance than that based only on pure SWCNTs yarns, making it an ideal energy‐storage device for wearable electronics.     

Unconventional Nanofabrication for Supramolecular Electronics

The scientific effort toward achieving a full control over the correlation between structure and function in organic and polymer electronics has prompted the use of supramolecular interactions to drive the formation of highly ordered functional assemblies, which have been integrated into real devices. In the resulting field of supramolecular electronics, self‐assembly of organic semiconducting materials constitutes a powerful tool to generate low‐dimensional and crystalline functional architectures. These include 1D nanostructures (nanoribbons, nanotubes, and nanowires) and 2D molecular crystals with tuneable and unique optical, electronic, and mechanical properties. Optimizing the (opto)electronic properties of organic semiconducting materials is imperative to harness such supramolecular structures as active components for supramolecular electronics. However, their integration in real devices currently represents a significant challenge to the advancement of (opto)electronics. Here, an overview of the unconventional nanofabrication techniques and device configurations to enable supramolecular electronics to become a real technology is provided. A particular focus is put on how single and multiple supramolecular fibers and gels as well as supramolecularly engineered 2D materials can be integrated into novel vertical or horizontal junctions to realize flexible and high‐density multifunctional transistors, photodetectors, and memristors, exhibiting a set of new properties and excelling in their performances.     

3D‐Printed Biomimetic Super‐Hydrophobic Structure for Microdroplet Manipulation and Oil/Water Separation

Biomimetic functional surfaces are attracting increasing attention for various technological applications, especially the superhydrophobic surfaces inspired by plant leaves. However, the replication of the complex hierarchical microstructures is limited by the traditional fabrication techniques. In this paper, superhydrophobic micro‐scale artificial hairs with eggbeater heads inspired by Salvinia molesta leaf was fabricated by the Immersed surface accumulation three dimensional (3D) printing process. Multi‐walled carbon nanotubes were added to the photocurable resins to enhance the surface roughness and mechanical strength of the microstructures. The 3D printed eggbeater surface reveals interesting properties in terms of superhydrophobilicity and petal effect. The results show that a hydrophilic material can macroscopically behave as hydrophobic if a surface has proper microstructured features. The controllable adhesive force (from 23 μN to 55 μN) can be easily tuned with different number of eggbeater arms for potential applications such as micro hand for droplet manipulation. Furthermore, a new energy‐efficient oil/water separation solution based on our biomimetic structures was demonstrated. The results show that the 3D‐printed eggbeater structure could have numerous applications, including water droplet manipulation, 3D cell culture, micro reactor, oil spill clean‐up, and oil/water separation.     

SnO2‐Based Nanomaterials: Synthesis and Application in Lithium‐Ion Batteries

The development of new electrode materials for lithium‐ion batteries (LIBs) has always been a focal area of materials science, as the current technology may not be able to meet the high energy demands for electronic devices with better performance. Among all the metal oxides, tin dioxide (SnO₂) is regarded as a promising candidate to serve as the anode material for LIBs due to its high theoretical capacity. Here, a thorough survey is provided of the synthesis of SnO₂‐based nanomaterials with various structures and chemical compositions, and their application as negative electrodes for LIBs. It covers SnO₂ with different morphologies ranging from 1D nanorods/nanowires/nanotubes, to 2D nanosheets, to 3D hollow nanostructures. Nanocomposites consisting of SnO₂ and different carbonaceous supports, e.g., amorphous carbon, carbon nanotubes, graphene, are also investigated. The use of Sn‐based nanomaterials as the anode material for LIBs will be briefly discussed as well. The aim of this review is to provide an in‐depth and rational understanding such that the electrochemical properties of SnO₂‐based anodes can be effectively enhanced by making proper nanostructures with optimized chemical composition. By focusing on SnO₂, the hope is that such concepts and strategies can be extended to other potential metal oxides, such as titanium dioxide or iron oxides, thus shedding some light on the future development of high‐performance metal‐oxide based negative electrodes for LIBs.     

Photo‐Induced Polymerization and Reconfigurable Assembly of Multifunctional Ferrocene‐Tyrosine

The photo‐induced reconfigurable assembly of nanostructures via the simultaneous noncovalent and covalent polymerization of a functional ferrocene‐tyrosine (Fc‐Y) molecule is reported. The Fc‐Y monomers can directly self‐assemble into nanospheres with a smooth surface driven by noncovalent interactions. By covalent photo‐crosslinking of the Fc‐Y monomers, the nanospheres transform spontaneously into hollow vesicles composed of hierarchically ordered lamellar structures. It is worth noting that the formed nanostructures exhibit both reducing property for in situ mineralization of gold nanoparticles with tunable biocatalytic behavior, and the redox activity for superior energy storage capacity. The measured energy storage capacity is 31 mAh g⁻¹ for the nanospheres, which is the highest value reported so far for peptide assemblages as supercapacitor. The results offer insights into the dynamic self‐assembly of highly ordered multifunctional materials with promising applications in catalysis, sensing, energy and biomedical fields.     

Modelling interwall interactions in carbon nanotubes: fundamentals and device applications

Carbon nanotubes are the most commonly used 'building blocks' of modern nanotechnology. Their unique mechanical and electronic properties, stability and functionality show great promise in creating functional devices on the nanometre scale. One of the great challenges in using this scale is the ability of physical manipulation of the components, such as their positioning and assembling. Strong correlation between the structure and mechanical interactions of the walls of carbon nanotubes provides self-regulation of their relative motion. This can be further exploited in low-friction and high-stiffness devices. In this paper, we present a condensed overview of the recent progress in fundamental understanding of nanomechanical and nanoelectromechanical behaviour of carbon nanotubes and their applications in nanodevices.