Carbon nanotube film synthesized from ethanol and its oxidation behavior in air

In this paper, we propose an efficient way to synthesize carbon nanotube films using ferrocene and ethanol. The as-grown film is free-standing, semi-transparent, and of macro scale size. The tubes in the film are mostly single- or double-walled. The oxidation behavior of the film is studied via Raman spectroscopy, and the result indicates that the inner wall of the double-walled tube is effectively protected from oxidation by the outer wall.

Synthesis of nitrogen-doped single-walled carbon nanotubes and monitoring of doping by Raman spectroscopy

Nitrogen-doped single-walled carbon nanotubes （CNx-SWNTs） with tunable dopant concentrations were synthesized by chemical vapor deposition （CVD）, and their structure and elemental composition were characterized by using transmission electron microscopy （TEM） in combination with electron energy loss spectroscopy （EELS）. By comparing the Raman spectra of pristine and doped nanotubes, we observed the doping-induced Raman G band phonon stiffening and 2D band phonon softening, both of which reflect doping-induced renormalization of the electron and phonon energies in the nan- otubes and behave as expected in accord with the n-type doping effect. On the basis of first principles calculations of the distribution of delocalized carrier density in both the pristine and doped nanotubes, we show how the n-type doping occurs when nitrogen heteroatoms are substitutionally incorporated into the honeycomb tube-shell carbon lattice.

Influence of Pretreatment Conditions of Stainless Steel Substrates on Field Emission Properties of Carbon Nanotubes Films

Carbon nanotubes (CNTs) are synthesized from methane and hydrogen gas mixture directly on stainless steel plates by microwave plasma chemical vapor deposition (MWPCVD).By varying pretreatment conditions of the substrates such as mechanically polishing and acid washing,it is found the polishing and acid washing can lower the turn-on field and improve the emission current density.The current density of the un-pretreated sample attains 1.2mA/cm 2,but the polished sample and polished acidly washed sample attain 3.2 and 2.75mA/cm 2,respectively,at the electric field of 6.25V/μm.

Raman spectroscopy of isolated carbyne chains confined in carbon nanotubes:Progress and prospects

Carbyne is an infinitely long linear chain of carbon atoms with sp1hybridization and the truly one-dimensional allotrope of carbon.While obtaining freestanding carbyne is still an open challenge,the study of confined carbyne,linear chains of carbon encapsulated in carbon nanotubes,provides a pathway to explore carbyne and its remarkable properties in a well-defined environment.In this review,we discuss the basics and recent advances in studying single confined carbyne chains by Raman spectroscopy,which is their primary spectroscopic characterization method.We highlight where single carbyne chain studies are needed to advance our understanding of confined carbyne as a material system and provide an overview of the open questions that need to be addressed and of those aspects currently under debate.

Wide temperature range,air stable,transparent,and self-powered photodetectors enabled by a hybrid film of graphene and singlewalled carbon nanotubes

Transparent photovoltaic devices(TPVDs)have attracted increasing attention in emerging electronic devices.As the application scenarios extend,there raise higher requirements regarding the stability and operating temperature range of TPVDs.In this work,a unique preparation strategy is proposed for air stable TPVD with a wide operating temperature range,i.e.,a nanoscale architecture termed as H-TPVD is constructed that integrates a free-standing and highly transparent conductive hybrid film of graphene and single-walled carbon nanotubes(G-SWNT TCF for short)with a metal oxide NiO/TiO_(2)heterojunction.The preparation approach is suitable for scaling up.Thanks to the excellent transparent conductivity of the freestanding G-SWNT hybrid film and the ultrathin NiO/TiO_(2)heterojunction(100 nm),H-TPVD selectively absorbs the ultraviolet(UV)band of sunlight and has a transparency of up to 71%in the visible light.The integrated nanoscale architecture manifests the significant holecollecting capability of the G-SWNT hybrid film and the efficient carrier generation and separation within the ultrathin NiO/TiO_(2)heterojunction,resulting in excellent performance of the H-TPVD with a specific detectivity of 2.7×10^(10) Jones.Especially,the freestanding G-SWNT TCF is a super stable and non-porous two-dimensional film that can insulate gas molecules,thereby protecting the surface properties of NiO/TiO_(2)heterojunctions and enhancing the stability of H-TPVD.Having subjected to 20,000 cycles and storage in air for three months,the performance parameters such as photo-response signal,output power,and specific detectivity show no noticeable degradation.In particular,the as-fabricated self-powered H-TPVD can operate over a wide temperature range from −180 to 300℃,and can carry out solar-blind UV optical communication in this range.In addition,the 4×4 array H-TPVD demonstrates clear optical imaging.These results make it possible for H-TPVD to expand its potential application scenarios.

The Dynamics of the Nucleation, Growth and Termination of Single-Walled Carbon Nanotubes from in situ Raman Spectroscopy During Chemical Vapor Deposition

The dynamics of the chemical vapor deposition(CVD)of single-walled carbon nanotubes(SWNTs)is extracted experimentally using in situ Raman spectroscopy.Nanotubes are grown using a thinlm cobalt catalyst and an ethanol precursor in a miniature hot walled reactor with optical access.Raman spectra at room temperature and at the growth temperature are compared for two growth temperatures.The evolution of the G-band,D-band,and radial breathing mode(RBM)is tracked at the growth temperature with time resolution of a few seconds.There are three identifiable phases in the evolution of the Raman signal intensity:an initial exponential increasing phase,a linear growth phase,and a saturation phase.In situ optical spectroscopy thus enables the study of nucleation,steady growth,and deactivation processes to be investigated separately in real time.The evolution curves for all bands(G,D,and RBM),when scaled,collapse onto the same curve,to within experimental uncertainty.

Measuring Thermal Conductivity of an Individual Carbon Nanotube Using Raman Spectroscopy

In this paper,a non-contact method based on Raman spectroscopy was used to measure the thermal conductivity of an individual single-walled carbon nanotube(SWCNT)and a multi-walled carbon nanotube(MWCNT).The effect of laser-induced heating on carbon nanotubes(CNTs)was considered.The local temperatures along the longitudinal direction of carbon nanotube were determined by Raman shift,combined with one-dimensional heat conduction model,and the thermal conductivity was finally obtained.The thermal conductivity of the SWCNT with a length of 25μm and a diameter of 1.34 nm decreases as the temperature increases in the measuring temperature range(316 K–378 K).The corresponding thermal conductivities change from 1651 W/(m·K)to 2423 W/(m·K);the thermal conductivities of the MWCNT with 40μm length and 9.2 nm diameter are within 1109–1700 W/(m·K)at 316 K–445 K.To further analyze the size effect on the thermal conductivity,molecular dynamics simulation has been carried out.The result shows that the thermal conductivity of an individual carbon nanotube increases with increasing nanotube length and eventually converges.This work is expected to provide some reference data for the studies of thermal properties of individual CNTs.

Laser Induced Changes of the Raman Spectra of Pristine and Poly(<i>tert</i>-Butyl Acrylate) Functionalized Carbon Nanotubes

Pristine and poly(tert-butyl acrylate) (PTBA) functionalized carbon nanotubes are continuously exposed to 2.41 eV laser irradiation while collecting Raman spectra. The loss of the intensity of the radial breathing modes (RBMs) of small metallic PTBA functionalized nanotubes is less than that of pristine nanotubes. A reduction of the intensity of the G? band of pristine SWNTs occurs such that the overall shape of the G band evolves to resemble that of the PTBA functionalized sample. Complementing the measurement of the ratio of intensities of the D and G bands, the laser-in- duced spectral changes provide another way to determine the sidewall functionalization of carbon nanotubes. The laser-induced changes of the G and RBM bands are consistent with the greater sidewall reactivity of small metallic nanotubes toward functionalization with PTBA and reaction with photosensitized oxygen.

Carbon nanotubes as conducting support for potential Mn-oxide electrocatalysts： Influences of pre-treatment procedures

Different oxygen and nitrogen containing functional groups were created on the surface of the multiwalled carbon nanotubes. The multi-walled carbon nanotubes were treated in ultrasonic bath with sulfuric or nitric acid. Furthermore the surface texture was modified by increase of the roughness. In particular after treatment with the oxidizing nitric acid, in comparison to the H2SO4 or ultra-sonic treated samples,craters and edges are dominating the surface structures. Manganese oxide was deposited on the multiwalled carbon nanotubes by precipitation mechanism. Various manganese oxides are formed during the deposition process. The samples were characterized by elemental analysis, microscopy, thermal analysis,Raman spectroscopy, and by the zeta potential as well as X-ray diffraction measurements. It was shown that the deposited manganese oxides are stabilized rather by surface texture of the multi-walled carbon nanotubes than by created functional groups.

Raman microscopy mapping for the purity assessment of chirality enriched carbon nanotube networks in thin- film transistors

With recent improvements in carbon nanotube separation methods, the accurate determination of residual metallic carbon nanotubes in a purified nanotube sample is important, particularly for those interested in using semiconducting single-walled carbon nanotubes （SWCNTs） in electronic device applications such as thin-film transistors （TFTs）. This work demonstrates that Raman microscopy mapping is a powerful characterization tool for quantifying residual metallic carbon nanotubes present in highly enriched semiconducting nanotube networks. Raman mapping correlates well with absorption spectroscopy, yet it provides greater differentiation in purity. Electrical data from TFTs with channel lengths of 2.5 and 5μ m demonstrate the utility of the method. By comparing samples with nominal purities of 99.0% and 99.8%, a clear differentiation can be made when evaluating the current on/off ratio as a function of channel length, and thus the Raman mapping method provides a means to guide device fabrication by correlating SWCNT network density and purity with TFT channel scaling.

Application of Raman spectroscopy in carbon nanotube-based polymer composites

Raman spectroscopy has been widely used to identify the physical properties of carbon nanotubes(CNTs),and to assess their functionalization as well as orientation.Recently,Raman spectroscopy has become a powerful tool to characterize the interfacial properties between CNTs and polymer matrices.This review provides an overview of micro-Raman spectroscopy of CNTs and its application in studying CNT reinforced polymer composites.Based on the specific Raman band shifts relating to the mechanical deformation of CNTs,Raman scattering can be used to evaluate the interactions between the CNTs and the surrounding polymer in the composites,and to detect the phase transitions of the polymer,and investigate the local stress state as well as the Young's modulus of the CNTs.Moreover,we also review the current progress of Raman spectroscopy in various CNT macroarchitectures(such as films,fibers as well as composite fibers).The microscale structural deformation of CNT macroarchitectures and strain transfer factors from macroscale architectures to microscale structures are inferred.Based on an in situ Raman-tensile test,we further predict the Young's modulus of the CNT macroarchitectures and reveal the dominating factors affecting the mechanical performances of the CNT macroarchitectures.

Threshold voltage tuning and printed complementary transistors and inverters based on thin films of carbon nanotubes and indium zinc oxide

Carbon nanotubes （CNTs） have emerged as an important material for printed macroelectronics. However, achieving printed complementary macroelectronics solely based on CNTs is difficult because it is still challenging to make reliable n-type CNT transistors. In this study, we report threshold voltage （Vth） tuning and printing of complementary transistors and inverters composed of thin films of CNTs and indium zinc oxide （IZO） as p-type and n-type transistors, respectively. We have optimized the Vth of p-type transistors by comparing Ti/Au and Ti/Pd as source/drain electrodes, and observed that CNT transistors with Ti/Au electrodes exhibited enhancement mode operation （Vth 〈 0）. In addition, the optimized In：Zn ratio offers good n-type transistors with high on-state current （Ion） and enhancement mode operation （Vth 〉 0）. For example, an In：Zn ratio of 2：1 yielded an enhancement mode n-type transistor with Vth - 1 V and Ion of 5.2 μA. Furthermore, by printing a CNT thin film and an IZO thin film on the same substrate, we have fabricated a complementary inverter with an output swing of 99.6% of the supply voltage and a voltage gain of 16.9. This work shows the promise of the hybrid integration of p-type CNT and n-type IZO for complementary transistors and circuits.

SERS activity of carbon nanotubes modified by silver nanoparticles with different particle sizes

A two-dimensional(2D)surface-enhanced Raman scattering(SERS)substrate is fabricated by decorating carbon nanotube(CNT)films with Ag nanoparticles(Ag NPs)in different sizes,via simple and low-cost chemical reduction method and self-assembling method.The change of Raman and SERS activity of carbon nanotubes/Ag nanoparticles(CNTs/Ag NPs)composites with varying size of Ag NPs are investigated by using rhodamine 6G(R6G)as a probe molecule.Meanwhile,the scattering cross section of Ag NPs and the distribution of electric field of CNTs/Ag NPs composite are simulated through finite difference time domain(FDTD)method.Surface plasmon resonance(SPR)wavelength is redshifted as the size of Ag NPs increases,and the intensity of SERS and electric field increase with Ag NPs size increasing.The experiment and simulation results show a Raman scattering enhancement factor(EF)of 108for the hybrid substrate.

Electron irradiation-induced change of structure and damage mechanisms in multi-walled carbon nanotubes

Owing to their unique structure and excellent electrical property, carbon nanotubes （CNTs） as an ideal candidate for making future electronic components have great application potentiality. In order to meet the requirements for space appli- cation in electronic components, it is necessary to study structural changes and damage mechanisms of multi-walled carbon nanotubes （MWCNTs）, caused by the irradiations of 70 and 110 keV electrons. In the paper, the changes of structure and damage mechanisms in the irradiated MWCNTs, induced by the irradiations of 70 and 110 keV electrons, are investigated. The changes in surface morphology and structure of the irradiated MWCNT film are characterized using scanning electron microscopy （SEM）, x-ray photoelectron spectroscopy （XPS）, Raman spectroscopy, x-ray diffraction analysis （XRD）, and electron paramagnetic resonance （EPR） spectroscopy. It is found that the MWCNTs show different behaviors in structural changes after 70 and 110 keV electron irradiation due to different damage mechanisms. SEM results reveal that the irra- diation of 70 keV electrons does not change surface morphology of the MWCNT film, while the irradiation of 110 keV electrons with a high fluence of 5 x 1015 cm-2 leads to evident morphological changes, such as the formation of a rough surface, the entanglement of nanotubes and the shrinkage of nanotubes. Based on Raman spectroscopy, XPS, and XRD analyses, it is confirmed that the irradiation of 70 keV electrons increases the interlayer spacing of the MWCNTs and disorders their structure through electronic excitations and ionization effects, while the irradiation of 110 keV electrons obviously reduces the interlayer spacing of the MWCNTs and improves their graphitic order through knock-on atom dis- placements. The improvement of the irradiated MWCNTs by 110 keV electrons is attributed to the restructuring of defect sites induced by knock-on atom displacements. EPR spectroscopic analyses reveal that the MWCNTs exposed to both 70 keV electrons and 110 keV electrons suffer ionization damage to some extent.

Incorporation of Nitrogen Into Amorphous Carbon Films Produced by Surface-Wave Plasma Chemical Vapor Deposition

In order to study the influence of nitrogen incorporated into amorphous carbon films, nitrogenated amorphous carbon films have been deposited by using surface wave plasma chemical vapor deposition under various ratios of N2/CH4 gas flow. Optical emission spectroscopy has been used to monitor plasma features near the deposition zone. After deposition, the samples are checked by Raman spectroscopy and x-ray photo spectroscopy (XPS). Optical emission intensities of CH and N atom in the plasma are found to be enhanced with the increase in the N2/CH4 gas flow ratio, and then reach their maximums when the N2/CH4 gas flow ratio is 5%. A contrary variation is found in Raman spectra of deposited films. The intensity ratio of the D band to the G band (Id/Ig) and the peak positions of the G and D bands all reach their minimums when the N2/CH4 gas flow ratio is 5%. These show that the structure of amorphous carbon films has been significantly modified by introduction of nitrogen.

Taguchi-Optimized Catalytic Growth of Carbon Nanotubes for Applications in Electro-Catalysis

Taguchi method, largely used to optimize processes controlled by manifold parameters, has been utilized to improve the synthesis of carbon nanotubes by chemical vapor deposition of isobutane. Analyzing results obtained in nine suitably designed reactions, the influence of synthesis （773-973 K）, calcinations （723-1,023 K） and reduction （773-973 K） temperatures and catalyst-support （alumina, magnesia or Na＋-exchanged K10 clay） on specific yield and crystallization degree （i.e., C sp2 content） of the nanotubes has been ranked. After critical examination and adjusting of conditions predicted to give optimal results, -50 g of nanotubes per gram of metal are obtained at 973 K over Fe/alumina catalysts calcined at 723 K and reduced at 773 K. Under the same conditions, highly crystallized nanotubes （with 73% of C sp2 bonds, as qualitatively estimated from Raman spectroscopy）, suitable for electro-catalysis applications, are synthesized over Fe/clay catalysts.

Surface functionalization of single-walled carbon nanotubes using metal nanoparticles

Surface functionalization of suspended single-walled carbon nanotubes(SWNTs) using metal(Au) nanoparticles(NPs) is reported.SWNTs are grown on three-dimensionally patterned substrates by thermal chemical vapor deposition and successfully functionalized with Au NPs.Ethylendiamine is mainly used to functionalize SWNTs surface with amino groups before introducing Au NPs.From Raman scattering spectroscopy of the Au-functionalized suspended SWNTs,enhanced Raman scattering properties are obtained.The results suggest that the attached Au NPs may contribute to the enhancement of resonant phenomena.By measuring the electric properties after each functionalization process,it is found that Au NPs act as electron acceptor to the amine functionalized SWNTs.

Spectroscopic Investigation of Modified Single Wall Carbon Nanotube (SWCNT)

We have investigated the effects of chemical treatment on Single Wall Carbon Nanotube (SWCNT) before and after being modified with HNO3/H2SO4 by Raman, FTIR and UV-Vis-NIR spectroscopy. The results show successful carboxylation of the CNT sidewalls as observed from FTIR and UV-Vis-NIR spectroscopy. This successful functionalization is achieved in 6-8 hrs of refluxing. We also report changes in the first and second order Raman spectra of SWNTs functionalized with oxygenated groups. During the experiment, we observe some important Raman features: Radial breathing mode (RBM), Tangential mode (G-band), and Disordered mode (D-band);which are affected due to the chemical oxidation of carbon nanotubes. We found that the ratio of D- to the G-band intensity (Id/Ig), increase after functionalization and the RBM mode in acid treated SWCNTs is almost disappeared.

Enhancement of Elastic Modulus of Epoxy Resin with Carbon Nanotubes

Nanocomposites consisting of multiwall carbon nanotubes (MWCNT) and epoxy resin were produced by a standard calendaring technique. In this study, 3% multiwall carbon nanotube particles were dispersed in epoxy resin by weight to produce the multiwall carbon nanotubes/epoxy composite. Nanohardness and Raman spectroscopy tests were used to obtain the modulus of elasticity and Raman intensity of MWCNTs/ epoxy resin composite. The results show that the Raman intensity increased with the increase of Raman shift and Raman intensity also affected with the reinforcement of multiwall carbon nanotubes and 1% exposure of laser power. Also, nanohardness increased with increase of modulus of elasticity, which indicated that the toughness of epoxy resin improved with the addition of multiwall carbon nanotubes.