Semiconductor with intrinsic spin: a hybrid structure of zigzag edge graphene nanoribbon/single‐walled carbon nanotube

A hybrid structure of n ‐ZGRN/(m,m)SWCNT, namely n ‐ZGNR‐(m,m)SWCNT, is predicted. It is found that the n ‐ZGNR‐(m,m)SWCNT is a ferromagnetic semiconductor with intrinsic spin in which the manipulation of spin‐polarized currents can be achieved just simply by applying a gate voltage. Moreover, compared to n ‐ZGNR, the n‐ ZGNR‐(m,m)SWCNT possesses enhanced local magnetic moment. Semiconductors with intrinsic spin represent a new direction in the exploration of materials for spintronics and good prospects for practical spintronic applications. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Plasmon‐enhanced Raman scattering by suspended carbon nanotubes

We report plasmon‐enhanced Raman scattering of the order of 10³ by a metallic carbon nanotube partially suspended inside a near‐field cavity. The tube is part of a small bundle, and is interfaced with an Au nanodisc dimer using a recently developed assembly scheme based on dielectrophoretic deposition. Spatially resolved Raman measurements with two excitation wavelengths and two orthogonal polarizations confirm that the enhancement arises from a 65 nm long suspended tube segment. We show that the orientation of the tube inside the cavity can be as effective for generating enhancement as placing the nanotube precisely in a plasmonic hotspot. Position and shape of the G‐peak show that the suspended part of the tube is free of strain and doped with a Fermi energy shift ≤40 meV. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Tuning the phase transition of ZnO thin films through lithography: an integrated bottom‐up and top‐down processing

An innovative approach towards the physico‐chemical tailoring of zinc oxide thin films is reported. The films have been deposited by liquid phase using the sol–gel method and then exposed to hard X‐rays, provided by a synchrotron storage ring, for lithography. The use of surfactant and chelating agents in the sol allows easy‐to‐pattern films made by an organic–inorganic matrix to be deposited. The exposure to hard X‐rays strongly affects the nucleation and growth of crystalline ZnO, triggering the formation of two intermediate phases before obtaining a wurtzite‐like structure. At the same time, X‐ray lithography allows for a fast patterning of the coatings enabling microfabrication for sensing and arrays technology.     

Silver‐decorated carbon nanotube networks as SERS substrates

We report on investigations upon a surface‐enhanced Raman scattering (SERS) substrate produced from a two‐dimensional single‐walled carbon nanotube (SWNT) network decorated with Ag nanoparticles. Using the strong and unique Raman spectrum of SWNTs as a reference, the SWNT/Ag nanostructure can be considered to provide two regions: one with an ultrasensitive SERS response for single‐molecule SERS (SMSERS) study; and another with uniform SERS enhancement over an area of several square millimeters for general SERS measurements. We report the appearance of an anomalous Raman feature at around 2180 cm⁻¹ in the high‐sensitivity region which exhibits the characteristics of SMSERS. The SERS performance of the uniform area was characterized using pyridine vapor adsorbed onto the substrate. The presence of the SWNT/Ag nanostructure enhanced the Raman intensity by over seven orders of magnitude, a factor comparable to or exceeding that obtained on SERS substrates reported by other groups. The results indicate great potential to produce highly sensitive, uniform SERS substrates via further fine‐tuning of the nanostructure. Copyright © 2011 John Wiley & Sons, Ltd.     

Fabrication of suspended graphene devices and their electronic properties

Suspended graphene devices are successfully fabricated by using a novel PMMA/MMA/PMMA tri-layer resist technique. The gap between graphene and dielectric substrate can be easily controlled by the thickness of the bottom PMMA layer, and no wet-etching with hazardous hydrofluoric acid is involved in our fabrication process. Electrical characterizations on suspended graphene devices are performed in vacuum when in-situ current annealing directly leads to a significant improvement on transport properties of graphene, i.e., the increase of carrier mobility with the reduction of width of Dirac peak. Our results make a new opportunity to study intrinsic properties of graphene.     

Bottom‐up engineering of diamond micro‐ and nano‐structures

Engineering nanostructures from the bottom up enables the creation of carefully sculpted complex structures that are not accessible via top down fabrication techniques, in particular, complex periodic structures for applications in photonics and sensing. In this work a proof of principle that bottom up approach can be adopted and utilized for sculpting devices from diamond is proposed and demonstrated. A realization of periodic structures is achieved by growing nanoscale single crystal diamond through a defined pattern. Optical wave‐guiding of a narrow band emission attributed to the SiV defects in diamond is demonstrated by overgrowth on a thin diamond membrane. In addition, an array of hexagonal microdisks with diameter sizes ranging from 1 to 4 μm is demonstrated. The bottom up approach for diamond opens up new avenues for devices fabrication and sculpting three dimensional structures.     

Site‐specific fabrication of graphitic microporous carbon terminated with ordered multilayer graphene walls

The site‐specific fabrication of metal‐incorporated graphitic microporous carbon terminated by highly ordered multilayer graphene walls via an ambient‐temperature vacuum‐based process is presented for the first time. Sputtering of Cr nano‐particles on the ultrathin amorphous carbon film manifests a dual effect of activation via dry‐etching by the sputtering plasma and of ‘knock‐on' inelastic collision between nanoparticles and C atoms for structural ordering. This novel and simple method is very useful for fabricating high surface area carbon nanostructures for hydrogen storage and clean energy applications. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

甲基红掺杂碳纳米管悬浮液的光限幅特性研究

利用实验的方法研究了甲基红掺杂碳纳米管悬浮液对波长为532 nm激光的光限幅效应.分析了样品厚度和入射激光重复频率对光限幅特性的影响,并与纯碳纳米管悬浮液的光限幅特性进行了比较.实验结果表明,对于线性透过率为60%（500 nm）的碳纳米管悬浮液,掺入甲基红后其沉淀速度明显减慢,限幅阈值由250 μJ降低为200 μJ;对于2和5 mm 厚度的样品,掺杂甲基红使碳纳米管悬浮液的箝位输出激光脉冲能量分别由45和20 μJ降低为35和9 μJ.     

甲基红掺杂碳纳米管悬浮液的光限幅特性研究

利用实验的方法研究了甲基红掺杂碳纳米管悬浮液对波长为532 nm激光的光限幅效应.分析了样品厚度和入射激光重复频率对光限幅特性的影响,并与纯碳纳米管悬浮液的光限幅特性进行了比较.实验结果表明,对于线性透过率为60%（500 nm）的碳纳米管悬浮液,掺入甲基红后其沉淀速度明显减慢,限幅阈值由250 μJ降低为200 μJ;对于2和5 mm 厚度的样品,掺杂甲基红使碳纳米管悬浮液的箝位输出激光脉冲能量分别由45和20 μJ降低为35和9 μJ. 关键词： 非线性光学 光限幅效应 甲基红 染料掺杂碳纳米管悬浮液     

Raman G‐mode of single‐wall carbon nanotube bundles under pressure

Raman studies of nanotubes under pressure have been a lively area of research. However, the results are not always as expected and at times have not been adequately explained. One example of the diversity of the results is the higher energy Raman mode (the graphitic mode, GM) shift to higher wavenumber under pressure. Here we report a new high‐pressure Raman study showing that the effects of the variation in the tube diameters and the pressure transmitting medium are both crucial for understanding the outcomes of such high‐pressure experiments. Copyright © 2011 John Wiley & Sons, Ltd.     

Single‐wall carbon nanotube interactions with copper‐oxamato building block of molecule‐based magnets probed by resonance Raman spectroscopy

The electronic interactions between the [Cu(opba)]²⁻ anions (where opba is orthophenylenebis (oxamato)) and single‐wall carbon nanotubes (SWCNTs) were investigated by resonance Raman spectroscopy. The opba can form molecular magnets, and the interactions of opba with SWCNTs can produce materials with very different magnetic/electronic properties. It is observed that the electronic interaction shows a dependence on the SWCNT diameter independent of whether they are metallic or semiconducting, although the interaction is stronger for metallic tubes. The interaction also is dependent on the amount of complex that is probably adsorbed on the carbon surface of the SWCNTs. Some charge transfer can be also occurring between the metallic complex and the SWCNTs. Copyright © 2012 John Wiley & Sons, Ltd.     

Polybenzimidazole‐decorated carbon nanotube: A high‐performance proton conductor

Interaction between negatively charged Nafion^® and a positively charged polybenzimidazole‐decorated carbon nanotube leads to the formation of an ionic complex with high charge density for proton conduction, which can lead to an improvement in transport properties. Here we investigate the high‐temperature and low‐humidity proton conductivity of this nanocomposite membrane as a potential membrane for fuel cell applications.

     

High‐temperature stability of suspended single‐layer graphene

We report in situ Joule heating on suspended single‐layer graphene in a transmission electron microscope (TEM). Thermally‐driven degradation of pre‐deposited nanoparticles on the membrane is monitored and used for local temperature estimation. By extrapolating the Joule heating power and temperature relation, we find that the suspended single‐layer graphene has exceptional thermal stability up to at least 2600 K. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

New features in the anti‐Stokes and Stokes Raman spectra of single‐walled carbon nanotubes that are highly separated into their semiconducting and metallic nanotube components

Surface‐enhanced Raman scattering studies were performed using nonresonant (514.5 nm) and resonant (676.4 nm) optical excitations on single‐walled carbon nanotubes thoroughly separated into semiconducting (pure 99%) and metallic (pure 98%) components. Regardless of the support (Au or Ag), the metallic nanotubes do not present an anomalous anti‐Stokes Raman emission. Regardless of whether an on‐resonant or off‐resonant optical excitation is used, only the semiconducting nanotubes produce an abnormal anti‐Stokes Raman emission that grows when increasing the excitation light intensity or temperature. The Raman studies under light polarized relative to the main nanotube axis demonstrate that only semiconducting nanotubes are sensitive toward changes in the polarization of the excitation light. Copyright © 2014 John Wiley & Sons, Ltd.     

Flexible Graphene‐, Graphene‐Oxide‐, and Carbon‐Nanotube‐Based Supercapacitors and Batteries

Flexible energy‐storage devices increasingly attract attention owing to their advantages of providing lightweight, portable, wearable, or implantable capabilities. Many efforts are made to explore the structures and fabrication processes of flexible energy‐storage devices for commercialization. Here, the most recent advances in flexible energy‐storage devices based on graphene, graphene oxide (GO), and carbon nanotubes (CNTs), are described, including flexible supercapacitors and batteries. First, properties, synthesis methods, and possible applications of those carbon‐based materials are described. Then, the development of carbon‐nanotube‐based flexible supercapacitors, graphene/graphene‐oxide‐based flexible supercapacitors, and graphene‐ and carbon‐nanotube‐based flexible battery electrodes are discussed. Finally, the future trends and perspectives in the development of flexible energy‐storage devices are highlighted.     

Changes in the vibrational modes of carbon nanotubes induced by electron‐beam irradiation: resonance Raman spectroscopy

Influence of electron‐beam (e‐beam) irradiation on multi‐walled (MW) and single‐walled (SW) carbon nanotube films grown by microwave chemical vapor deposition technique is investigated. These films were subjected to an e‐beam energy of 50 keV from a scanning electron microscope for 2.5, 5.5, 8.0, and 15 h, and to 100 and 200 keV from a transmission electron microscope for a few minutes to ∼2 h continuously. Such conditions resemble an increased temperature and pressure regime enabling a degree of structural fluidity. To assess structural modifications, they were analyzed prior to and after irradiation using resonance Raman spectroscopy (RRS) in addition to in situ monitoring by electron microscopy. The experiments showed that with extended exposures, both types of nanotubes displayed various local structural instabilities including pinching, graphitization/amorphization, and formation of an intramolecular junction (IMJ) within the area of electron beam focus possibly through amorphous carbon aggregates. RRS revealed that irradiation generated defects in the lattice as quantified through (1) variation of the intensity of radial breathing mode (RBM), (2) intensity ratio of D to G band (I_D/I_G), and (3) positions of the D and G bands and their harmonics (D* and G*) and combination bands (D + G). The increase in the defect‐induced D band intensity, quenching of RBM intensity, and only a slight increase in G band intensity are some of the implications. The MW nanotubes tend to reach a state of saturation for prolonged exposures, while the SW ones transform from a semiconducting to a quasi‐metallic character. Softening of the q = 0 selection rule is suggested as a possible reason to explain these results. Furthermore, these studies provide a contrasting comparison between MW and SW nanotubes. Copyright © 2006 John Wiley & Sons, Ltd.     

A novel fabrication method of CNT‐CP composite single nanowires self‐templated by dielectrophoresis and electropolymerization

A new method for fabricating carbon nanotube‐conducting polymer (CNT‐CP) composite single nanowires is reported. The method developed is highly efficient, reliable, and economical because it obviates the time consuming process of template fabrication and the post‐synthesis task of positioning nanowires. Single nanowires with diameters of 50‐500 nm are fabricated between electrodes, self‐templated by dielectrophoresis and electropolymerization. Fabrication of an individually addressed nanowire array with cantilever electrodes on a microchip is demonstrated.

     

Experimental characterization of temperature‐dependent electron transport in single‐wall multi‐tube carbon nanotube transistors

Current–voltage, radio‐frequency (RF) and noise characteristics of single‐wall multi‐tube carbon nanotube (CNT) transistors were measured at cryogenic temperatures. Compared to an ambient temperature (T_a) of 300 K, only a slight drain current increase at T_a = 77 K was observed. In addition, a weak dependence of the maximum value of the current gain cut‐off frequency (f_T) on T_a was obtained, indicating that f_T is rather limited by the device intrinsic quantum and extrinsic capacitances than by an improved mobility due to reduced optical phonon scattering at low T_a. A noise analysis of the devices at T_a = 10 K reveals that the noise factor (NF) improvement at very low temperatures is related to the reduced Nyquist noise of all resistive transistor noise contributors. Since the main noise source in CNTFETs is the shot noise, NF remains comparatively high even at T_a = 10 K.

     

Raman imaging and stress quantification in self‐assembled graphene oxide fiber ‘Latin Letters’

To probe the intrinsic stress distribution in terms of spatial Raman shift (ω) and change in the phonon linewidth (Γ), here we analyze self‐assembled graphene oxide fibers (GOF) ‘Latin letters’ by confocal Raman spectroscopy. The self‐assembly of GOF ‘Latin letters’ has been explained through surface tension, π–π stacking, van der Waals interaction at the air–water interface and by systematic time‐dependent investigation using field emission scanning electron microscopy analysis. Intrinsic residual stress due to structural joints and bending is playing a distinct role affecting the E_2g mode (G band) at and away from the physical interface of GOF segments with broadening of phonon linewidth, indicating prominent phonon softening. Linescan across an interface of the GOF ‘letters’ reveals Raman shift to lower wavenumber in all cases but more so in ‘Z’ fiber exhibiting a broader region. Furthermore, intrinsic stress homogeneity is observed for ‘G’ fiber distributed throughout its curvature with negligible shift corresponding to E_2g mode vibration. This article demonstrates the significance of morphology in stress distribution across the self‐assembled and ‘smart‐integrable’ GOF ‘Latin letters’. Copyright © 2016 John Wiley & Sons, Ltd.