Selective Enhancement of Photoluminescence in Filled Single‐Walled Carbon Nanotubes

The insertion of organometallic molecules into the hollow core of single‐walled carbon nanotubes can drastically change their properties. Using biocompatible standardized suspensions of pristine, opened, and filled nanotubes, a very selective enhancement of the photoluminescence and optical absorption is observed. Via ferrocene encapsulation, the PL signal increases almost by a factor of three for tubes with chiralities such as (8,6) and (9,5). This behavior is attributed to a local electron charge transfer from the ferrocene molecules that balances out the p‐type doping of the nanotubes resulting from the modified charge distribution of the surfactant molecules and the opening process. The near infrared photoluminescence of the nanotubes in solution is strongly enhanced when ferrocene is encapsulated. The diameter‐dependent charge transfer is additionally confirmed by first principles calculations. These findings highlight an essential ingredient to optimize the application of solvated nanotubes, for instance, as in–vivo near infrared sensors in biomedical research.     

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.     

Solid‐State Approach for Fabrication of Photostable,Oxygen‐Doped Carbon Nanotubes

A novel procedure for effective fabrication of photostable oxygen‐doped single‐walled carbon nanotubes (SWCNTs) in solid‐state matrices has been developed. SWCNTs drop‐cast on various types of substrates are coated with oxide dielectric thin films by electron‐beam evaporation. Single tube photoluminescence spectroscopy studies performed at room and cryogenic temperatures reveal that such thin film‐coated tubes exhibit characteristic spectral features of oxygen‐doped SWCNTs, indicating the oxide thin film coating process leads to oxygen doping of the tubes. It is also found that the doping efficiency can be effectively controlled by the thin film deposition time and by the types of surfactants wrapping the SWCNTs. Moreover, aside from being the doping agent, the oxide thin film also serves as a passivation layer protecting the SWCNTs from the external environment. Comparing the thin film coated SWCNTs with oxygen‐doped tubes prepared via ozonolysis, the former exhibit significantly higher photostability and photoluminescence on‐time. Therefore, this one‐step deposition/oxygen‐doping procedure provides a possible route toward scalable, versatile incorporation of highly photostable oxygen‐doped SWCNTs in novel optical and optoelectronic devices.     

In‐Situ Vis–Near‐Infrared and Raman Spectroelectrochemistry of Double‐Walled Carbon Nanotubes

Double‐walled carbon nanotubes (DWCNTs) are studied using in‐situ visible–near‐infrared (vis‐NIR) and in‐situ Raman spectroelectrochemistry. Electrochemical vis‐NIR spectroscopy reveals a complex picture of DWCNTs due to the overlap of the features of the inner and outer tubes and possible optical transitions, which are not predicted by the simple tight‐binding model. The optical transitions are bleached upon electrochemical doping. This is qualitatively understood to be a consequence of the Fermi‐level shift by the applied potential relative to the van Hove singularity. In‐situ Raman spectra are quenched by the applied cathodic/anodic potentials due to the loss of resonance by electrochemical charging. The electrochemical tuning of Raman spectra proceeds distinctly for inner and outer tubes. While the bands of outer tubes rapidly follow the potential change, the features of inner tubes respond relatively slowly to electrochemical perturbations. The Raman D‐mode of DWCNTs was found to be bifurcated upon electrochemical charging, which is similar to the behavior of the tangential displacement mode. Ionic liquids are good electrolytes for the spectroelectrochemistry of DWCNTs, even at extreme applied potentials. They allow the deconvolution of the tangential modes of the inner and outer tubes at both cathodic and anodic doping.     

Growth of Single‐Walled Carbon Nanotubes from Microcontact‐Printed Catalyst Patterns on Thin Si3N4 Membranes

Single‐walled carbon nanotubes have been grown by chemical vapor deposition from methane and hydrogen on catalyst patterns prepared by microcontact printing on 20 nm thick silicon nitride substrates. A higher yield of single‐walled carbon nanotubes was obtained by the simple expedient of introducing hydrogen during deposition. Based on atomic force microscopy and transmission electron microscopy measurements, we found that high‐quality single‐walled carbon nanotubes with a broad diameter distribution were obtained.     

Sensing of Damage Mechanisms in Fiber‐Reinforced Composites under Cyclic Loading using Carbon Nanotubes

The expanded use of advanced fiber‐reinforced composites in structural applications has brought attention to the need to monitor the health of these structures. It has been established that adding carbon nanotubes to fiber‐reinforced composites is a promising way to detect the formation of microscale damage. Because carbon nanotubes are three orders of magnitude smaller than traditional advanced fibers, it is possible for nanotubes to form an electrically conductive network in the polymer matrix surrounding the fibers. In this work, multi‐walled carbon nanotubes are dispersed into epoxy and infused into a glass‐fiber preform to form a network of in situ sensors. The resistance of the cross‐ply composite is measured in real‐time during incremental cyclic tensile loading tests to evaluate the damage evolution and failure mechanisms in the composite. Edge replication is conducted to evaluate the crack density after each cycle, and optical microscopy is utilized to study the crack mode and growth. The evolution of damage can be clearly identified through the damaged resistance parameter. Through analyzing the damaged resistance response curves with measurements of transverse crack density and strain, the transition between different failure modes can be identified. It is demonstrated that the integration of an electrically conducting network of carbon nanotubes in a glass fiber composite adds unique damage‐sensing functionality that can be utilized to track the nature and extent of microstructural damage in fiber composites.     

Polyazines and Polyazomethines with Didodecylthiophene Units for Selective Dispersion of Semiconducting Single‐Walled Carbon Nanotubes

Polymer wrapped single‐walled carbon nanotubes (SWNTs) have been demonstrated to be a very efficient technique to obtain high purity semiconducting SWNT solutions. However, the extraction yield of this technique is low compared to other techniques. Poly‐alkyl‐thiophenes have been reported to show higher extraction yield compare to polyfluorene derivatives. Here, the affinity for semiconducting SWNTs of two polymers with a backbone containing didodecylthiophene units interspersed with N atoms is reported. It is demonstrated that one of the polymers, namely, poly(2,5‐dimethylidynenitrilo‐3,4‐didodecylthienylene) (PAMDD), has very high semiconducting SWNT extraction yield compared to the poly(3,4‐didodecylthienylene)azine (PAZDD). The dissimilar wrapping efficiency of these two polymers for semiconducting SWNTs is attributed to the interplay between the affinity for the nitrogen atoms of the highly polarizable walls of SWNTs and the mechanical flexibility of the polymer backbones. Photoluminescence (PL) measurements demonstrate the presence of metallic tubes and SWNT bundles in the sample selected with PAZDD and higher purity of SWNT‐PAMDD samples. The high purity of the semiconducting SWNTs selected by PAMDD is further demonstrated by the high performance of the solution‐processed field‐effect transistors (FETs) fabricated using a blade coating technique, which exhibit hole mobilities up to 33.3 cm² V^?1 s^?1 with on/off ratios of 10⁶.     

Significantly Enhanced Photoluminescence of Doped Polymer‐Metal Hybrid Nanotubes

We report on the significantly enhanced photoluminescence (PL) of hybrid double‐layered nanotubes (HDLNTs) consisting of poly(3‐methylthiophene) (P3MT) nanotubes with various doping levels enveloped by an inorganic, nickel (Ni) metal nanotube. From laser confocal microscopy PL experiments on a single strand of the doped‐P3MT nanotubes and of their HDLNTs, the PL peak intensity of the HDLNT systems increased remarkably up to ～350 times as the doping level of the P3MT nanotubes of the HDLNTs increased, which was confirmed by measurements of the quantum yield. In a comparison of the normalized ultraviolet and visible absorption spectra of the doped‐P3MT nanotubes and their HDLNTs, new absorption peaks corresponding to surface‐plasmon (SP) energy were created at 563 and 615 nm after the nanoscale Ni metal coating onto the P3MT nanotubes, and their intensity increased on increasing the doping level of the P3MT nanotube. The doping‐induced bipolaron peaks of the HDLNTs of doped‐P3MT/Ni were relatively reduced, compared with those of the doped‐P3MT nanotubes before the Ni coating, due to the charge‐transfer effect in the SP‐resonance (SPR) coupling. Both energy‐transfer and charge‐transfer effects due to SP resonance contributed to the very‐large enhancement of the PL efficiency of the doped‐P3MT‐based HDLNTs.     

Simple Salt‐Coordinated n‐Type Nanocarbon Materials Stable in Air

After more than three decades of molecular and carbon‐based electronics, the creation of air‐ and thermally stable n‐type materials remains a challenge in the development of future p/n junction devices such as solar cells and thermoelectric modules. Here a series of ordinary salts are reported such as sodium chloride (NaCl), sodium hydroxide (NaOH), and potassium hydroxide (KOH) with crown ethers as new doping reagents for converting single‐walled carbon nanotubes to stable n‐type materials. Thermoelectric analyses reveal that these new n‐type single‐walled carbon nanotubes display remarkable air stability even at 100 °C for more than 1 month. Their thermoelectric properties with a dimensionless figure‐of‐merit (ZT) of 0.1 make these new n‐type single‐walled carbon nanotubes a most promising candidate for future n‐type carbon‐based thermoelectric materials.     

Sub‐kilogram‐Scale One‐Pot Synthesis of Highly Luminescent and Monodisperse Core/Shell Quantum Dots by the Successive Injection of Precursors

The one‐pot synthesis of core/shell quantum dots (QDs) represents an attractive alternative to conventional synthesis techniques, where the core CdSe QDs are first purified and then an epitaxial shell of the desired thickness is obtained by the slow addition of shell precursors to a solution of the purified QDs at high temperature. We have developed a one‐pot synthesis procedure involving the successive injection of deliberately selected core‐ and shell‐forming reagents at appropriate temperatures. Sub‐kilogram quantities of highly luminescent and monodisperse core/shell QDs with desirable optical properties (full width at half maximum of photoluminescence (PL) band is ca. 30 nm) have been produced by the sequential growth of the core and shell in a controlled manner. This one‐pot method has also been extended to form water‐soluble core/double‐shell CdSe/ZnSe/ZnS QDs exhibiting high PL efficiency and stability.     

Hierarchical Composites of Single/Double‐Walled Carbon Nanotubes Interlinked Flakes from Direct Carbon Deposition on Layered Double Hydroxides

Three‐dimensional hierarchical nanocomposites consisting of one‐dimensional carbon nanotubes (CNTs) and two‐dimensional lamellar flakes (such as clay, layered double hydroxides) show unexpected properties for unique applications. To achieve a well‐designed structure with a specific function, the uniform distribution of CNTs into the used matrix is a key issue. Here, it is shown that a hierarchical composite of single/double‐walled CNTs interlinked with two‐dimensional flakes can be constructed via in‐situ CNT growth onto layered double hydroxide (LDH) flakes. Both the wall number and diameter of the CNTs and the composition of the flakes can be easily tuned by changing the proportion of the transition metal in the LDH flakes. Furthermore, a structure with continuously interlinked CNT layers alternating with lamellar flakes is obtained after compression. The hierarchical composite is demonstrated to be an excellent filler for strong polyimide films. This study indicates that LDH is an extraordinary catalyst for the fabrication of hierarchical composites with high‐quality single/double‐walled CNTs. The as‐obtained CNTs/calcined LDHs nanocomposite is a novel structural platform for the design of mechanically robust materials, catalysts, ion‐transportation, energy‐conversion, and other applications.     

Highly Conductive Redox Protein–Carbon Nanotube Complex for Biosensing Applications

The integration of redox proteins with nanomaterials has attracted much interest in the past years, and metallic single‐walled carbon nanotubes (SWNTs) have been introduced as efficient electrical wires to connect biomolecules to metal electrodes in advanced nano‐biodevices. Besides preserving biofunctionality, the protein–nanotube connection should ensure appropriate molecular orientation, flexibility, and efficient, reproducible electrical conduction. In this respect, yeast cytochrome c redox proteins are connected to gold electrodes through lying‐down functionalized metallic SWNTs. Immobilization of cytochromes to nanotubes is obtained via covalent bonding between the exposed protein thiols and maleimide‐terminated functional chains attached to the carbon nanotubes. A single‐molecule study performed by combining scanning probe nanoscopies ascertains that the protein topological properties are preserved upon binding and provides unprecedented current images of single proteins bound to carbon nanotubes that allow a detailed I–V characterization. Collectively, the results point out that the use as linkers of suitably functionalized metallic SWNTs results in an electrical communication between redox proteins and gold electrodes more efficient and reproducible than for proteins directly connected with metal surfaces.     

Efficient Isolation and Solubilization of Pristine Single‐Walled Nanotubes in Bile Salt Micelles

We have investigated a wide variety of surfactants for their efficiency in dissolving isolated single‐walled carbon nanotubes (SWNTs) in water. In doing so, we have completely avoided the harsh chemical or mechanical conditions, such as acid or ultrasonic treatments, that are known to damage SWNTs. Bile salts in particular are found to be exceptionally effective in dissolving individual tubes, as evidenced by highly resolved optical absorption spectra, bright bandgap fluorescence, and the unprecedented resolution (～ 2.5 cm^–1) of the radial breathing modes in Raman spectra. This is attributed to the formation of very regular and stable micelles around the nanotubes providing an unusually homogeneous environment. Quantitative information concerning the degree of solubilization is obtained from absorption spectroscopy.     

Mechanical Properties of Functionalized Single‐Walled Carbon‐Nanotube/Poly(vinyl alcohol) Nanocomposites

Nanocomposites based on semi‐crystalline poly(vinyl alcohol) (PVA) and well‐dispersed chemically functionalized single‐walled carbon nanotubes are combined through simple mixing. The interaction between the nanotubes and the polymer matrix is studied using optical and thermal methods. Significant enhancement of the mechanical properties is obtained for the functionalized‐nanotube‐based composites. These results imply that promoting nanotube dispersion and strong interfacial bonding through adequate functionalization of nanotubes improves the load transfer from the matrix to the reinforcing phase.     

Tuning and Enhancing Photoluminescence of Light‐Emitting Polymer Nanotubes through Electron‐Beam Irradiation

A new method for the tuning and enhancing photoluminescence (PL) characteristics of light emitting poly (3‐methylthiopnehe) (P3MT) nanotubes through E‐beam irradiation under atmospheric environments is reported. An E‐beam generated from a linear electron accelerator (1 MeV, 1.6 × 10¹³–8.0 × 10¹⁶ electrons cm^–2) is irradiated onto P3MT nanotubes including an Al₂O₃ template. From laser confocal microscope (LCM) PL experiments, significant enhancements in the PL intensity—up to about 90 times of an isolated single strand of the E‐beam irradiated P3MT nanotubes—are observed. The luminescent color of the P3MT nanotubes changes from green to red color depending on the variation of E‐beam dosage. These results might originate from the de‐doping effect and the conformational modification through E‐beam irradiations. Conformational changes of the E‐beam irradiated P3MT nanotubes are confirmed by LCM single Raman and ultraviolet‐visible (UV/Vis) absorption spectra. From UV/Vis absorption spectra, it is observed that the π–π* transition peak and the doping induced bipolaron peaks of the P3MT nanotubes dramatically vary with E‐beam irradiating conditions.     

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.     

Fabrication and Optical Characteristics of Position‐Controlled ZnO Nanotubes and ZnO/Zn0.8Mg0.2O Coaxial Nanotube Quantum Structure Arrays

The position‐controlled growth and structural and optical characteristics of ZnO nanotubes and their coaxial heterostructures are reported. To control both the shape and position of ZnO nanotubes, hole‐patterned SiO₂ growth‐mask layers on Si(111) substrates with GaN/AlN intermediate layers using conventional lithography are prepared. ZnO nanotubes are grown only on the hole patterns at 600 °C by catalyst‐free metal–organic vapor‐phase epitaxy. Furthermore, the position‐controlled nanotube growth method allows the fabrication of artificial arrays of ZnO‐based coaxial nanotube single‐quantum‐well structures (SQWs) on Si substrates. In situ heteroepitaxial growth of ZnO and Zn_0.8Mg_0.2O layers along the circumference of the ZnO nanotube enable an artificial formation of quantum‐well arrays in a designed fashion. The structural and optical characteristics of the ZnO nanotubes and SQW arrays are also investigated using synchrotron radiation X‐ray diffractometry and photoluminescence and cathodoluminescence spectroscopy.     

Tin Dioxide Sensing Layer Grown on Tubular Nanostructures by a Non‐Aqueous Atomic Layer Deposition Process

A new atomic layer deposition (ALD) process for nanocrystalline tin dioxide films is developed and applied for the coating of nanostructured materials. This approach, which is adapted from non‐hydrolytic sol‐gel chemistry, permits the deposition of SnO₂ at temperatures as low as 75 °C. It allows the coating of the inner and outer surface of multiwalled carbon nanotubes with a highly conformal film of controllable thickness. The ALD‐coated tubes are investigated as active components in gas‐sensor devices. Due to the formation of a p‐n heterojunction between the highly conductive support and the SnO₂ thin film an enhancement of the gas sensing response is observed.     

Nitrogen‐Doped Single‐Walled Carbon Nanotubes Grown on Substrates: Evidence for Framework Doping and Their Enhanced Properties

Nitrogen‐doped single‐walled carbon nanotubes (SWCNTs) are synthesized directly on silicon and quartz substrates through a normal chemical vapor deposition (CVD) method. Thermogravimetry mass spectrometry measurements and Raman spectroscopy give firm evidence for framework nitrogen doping. X‐ray‐photoelectron‐spectroscopy analysis further obtains the bonding style of the nitrogen atoms in the carbon framework. The nitrogen doping significantly changes the properties of the SWCNTs. All of the tubes behave like metallic tubes in field‐effect transistors. The doped nitrogen atoms introduce a stronger affinity for the SWCNTs to metal nanoparticles. Compared with pristine SWCNTs, the nitrogen‐doped tubes show enhanced sensitivity and selectivity for electrochemical detection of some electrophilic species including O₂, H₂O₂, and Fe³⁺. They also present improved electrocatalytic activity for oxygen reduction. These unique properties of the nitrogen‐doped SWCNTs endow them with important potential applications in various fields.     

异质结构材料的傅立叶变换光萤光谱的测试与分析

介绍了傅立叶交换光萤光谱测试的基本原理；报道了用ＰＬ６１２０设备测得的一些典型的异质结构材料光萤光谱；分析和讨论了光萤光双峰结构、光萤光谱异常温度特性等问题；指出了异质界面上原子排列无序和内应力是造成这些异常现象的物理原因。