Tunable Schottky diodes fabricated from crossed electrospun SnO2/PEDOT-PSSA nanoribbons

Schottky diodes have been fabricated on doped Si/SiO₂ substrates in air, by simply crossing individual electrospun tin oxide (SnO₂) and poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) (PEDOT-PSSA) nanoribbons. The conductivity of PEDOT-PSSA was ∼6 S/cm with no observable field effect, while SnO₂ exhibited n-doped field effect behavior with a charge mobility of ∼3.1 cm²/V-s. The diodes operate in air or in vacuum, under ambient illumination or in the dark, with low turn-on voltages and device parameters that are tunable via a back gate bias or a UV light source. Their unique design involves a highly localized active region that is completely exposed to the surrounding environment, making them potentially attractive for use as sensors. The standard thermionic emission model of a Schottky junction was applied to analyze the forward bias diode characteristics and was successfully tested as a half wave rectifier.     

Preparation and characterization of poly(3-octylthiophene)/carbon fiber thermoelectric composite materials

Poly(3-alkylthiophene) (P3AT) with a high Seebeck coefficient has recently been reported. However, P3AT/inorganic conductive composites exhibit relatively poor thermoelectric performance because of their low electrical conductivity. In this work, carbon fiber sheets with a high electrical conductivity were chosen as the inorganic phase, and poly(3-octylthiophene)(P3OT)/carbon fiber composites were prepared by casting P3OT solution onto the carbon fiber sheets. The carbon fiber sheets incorporated into the composites can provide good electrical conductivity, and P3OT can provide a high Seebeck coefficient. The highest power factor of 7.05 μW m⁻¹ K⁻² was obtained for the composite with 50 wt% P3OT. This work suggests a promising method for preparing large-scale thermoelectric composites with excellent properties.     

Charge-transfer interaction in single-walled carbon nanotubes with tetrathiafulvalene and their applications

We observed that single-walled carbon nanotube (SWNT) was aligned in the presence of TTF This alignment was induced by a specific interaction between SWNT and tetrathiafulvalene (TTF), a well-known organic donor. The interaction between the two molecules can be explained by a charge-transfer, which was confirmed by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The binding energies of S (2P1/2) and S (2P3/2) were shifted from 163.0 eV and 164.1 eV to 163.9 eV and 165.1 eV, respectively. In Raman spectra of the SWNT-TTF, three peaks of SWNT in radial breathing mode were also upshifted by 4-5 cm(-1). The charge-transfer interaction also contributed in modifying the electronic structure of SWNT and furthermore enhanced the electrical conductivity of SWNT. A more conductive thin film was fabricated using the SWNT-TTF Four-probe measurement revealed that the surface resistance of the SWNT-TTF film was reduced to 4.359 omega at room temperature while that of SWNT film was 6.894 omega. These results enable carbon nanotubes to be utilized more for practically for industrial applications in fabricating peculiar nano-sized building blocks.     

Photoelectrochemical reactions of electrodes modified with composites between conjugated polymer or ruthenium complex and single-walled carbon nanotubes

Composite materials between conjugated polymer; poly[2-methoxy-5-(2'-ethylhexyloxy)-1.4-phenylene vinylene] (MEHPPV), or ruthenium(II)-tris(2,2'-bipyridine) (Ru(bpy)₃²⁺)-poly(sodium 4-styrenesulfonate) (PSS) complex and single-walled carbon nanotubes (SWNTs) were fabricated using polymer wrapping method. Formation of SWNT/MEHPPV or SWNT/PSS/Ru(bpy)₃²⁺ composite was confirmed by absorption and fluorescence spectra, and AFM images. Electrode modified with SWNT/MEHPPV or SWNT/PSS/Ru(bpy)₃²⁺ composite was prepared by casting from DMF solution of SWNT/MEHPPV or aqueous solution of SWNT/PSS/Ru(bpy)₃²⁺. The electrode modified with SWNT/MEHPPV or SWNT/PSS/Ru(bpy)₃²⁺ composite showed photocurrent response due to photoexcitation of MEHPPV or Ru(bpy)₃²⁺. The photocurrents are ascribed to photoinduced electron-transfer reaction from excited state of MEHPPV or Ru(bpy)₃²⁺ to SWNT.     

Quantitative analysis of the (n,m) abundance of single-walled carbon nanotubes dispersed in ionic liquids by optical absorption spectra

Room temperature ionic liquids (ILs) of imidazolium ions were found to be ideal media for dispersing single-walled carbon nanotubes (SWNTs) at relatively high content and for studying their intrinsic properties. Comparing to other dispersion methods IL dispersion do not involve in extensive ultrasonication and centrifugation, thus can reflect the real chiral composition and abundance distribution of the original raw SWNT samples. Optical absorption spectra of 1-N-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF₆])-dispersed SWNTs at different concentrations are performed based on direct and precise weighing the mass of the SWNT samples. An excellent linear relationship of the absorbance with respect to SWNT concentration is observed not only in a large concentration scale but also over a wide wavelength range. By deconvolution of the absorption spectra in the region of the first subbands transition of semiconducting SWNTs (E₁₁^S region, 800–1400 nm) into individual bands with (n,m) assignment in good agreement with fluorescence spectra, the relative abundance of 12 different semiconducting chiralities is analyzed quantitatively. It is found that the relative abundance of semiconducting SWNTs follows an exponential trend with respect to chiral angle. No clear dependence of the relative abundance on tube diameter is observed.     

Inkjet printing of single-walled carbon nanotube/RuO<Subscript>2</Subscript> nanowire supercapacitors on cloth fabrics and flexible substrates

Single-walled carbon nanotube (SWNT) thin film electrodes have been printed on flexible substrates and cloth fabrics by using SWNT inks and an off-the-shelf inkjet printer, with features of controlled pattern geometry (0.4–6 cm²), location, controllable thickness (20–200 nm), and tunable electrical conductivity. The as-printed SWNT films were then sandwiched together with a piece of printable polymer electrolyte to form flexible and wearable supercapacitors, which displayed good capacitive behavior even after 1,000 charge/discharge cycles. Furthermore, a simple and efficient route to produce ruthenium oxide (RuO₂) nanowire/SWNT hybrid films has been developed, and it was found that the knee frequency of the hybrid thin film electrodes can reach 1,500 Hz, which is much higher than the knee frequency of the bare SWNT electrodes (˜158 Hz). In addition, with the integration of RuO₂ nanowires, the performance of the printed SWNT supercapacitor was significantly improved in terms of its specific capacitance of 138 F/g, power density of 96 kW/kg, and energy density of 18.8 Wh/kg. The results indicate the potential of printable energy storage devices and their significant promise for application in wearable energy storage devices.      

Visible-light-driven photocatalysis with dopamine-derivatized titanium dioxide/<Emphasis Type="Italic">N</Emphasis>-doped carbon core/shell nanoparticles

Titanium dioxide/N-doped carbon core/shell nanoparticles enabling efficient visible-light-driven photocatalytic degradation of rhodamine B, considered a model compound for water-soluble environmental pollutants, were successfully prepared by the carbonization of dopamine-grafted TiO₂ nanoparticles. These precursor nanoparticles were prepared via simple ligand-to-metal charge transfer (LMCT) between TiO₂ nanoparticles and dopamine. Owing to the incorporation of Ti–O–C chelating bonds and the subsequent narrowing of the optical band gap, the dopamine-derivatized photocatalyst demonstrated enhanced activity compared with that of commercial photocatalysts and promoted the photocatalytic degradation of rhodamine B under both UV light and visible light. This LMCT-mediated incorporation of thin amorphous N-doped carbon shells onto the surface of semiconducting photocatalysts may be widely applicable for the generation of novel and robust hybrid materials with enhanced photocatalytic activities for many applications.     

Composite electronic materials based on poly(3,4-propylenedioxythiophene) and highly charged poly(aryleneethynylene)-wrapped carbon nanotubes for supercapacitors

Supercapacitor charge storage media were fabricated using the semiconducting polymer poly(3,4-propylenedioxythiophene) (PProDOT) and single-walled carbon nanotubes (SWNTs) that were helically wrapped with ionic, conjugated poly[2,6-{1,5-bis(3-propoxysulfonicacidsodiumsalt)}naphthylene]ethynylene (PNES). These PNES-wrapped SWNTs (PNES-SWNTs) enable efficient dispersion of individualized nanotubes in a wide range of organic solvents. PNES-SWNT film-modified Pt electrodes were prepared by drop casting PNES-SWNT suspensions in MeOH; high stability, first-generation PProDOT/PNES/SWNT composites were realized via electropolymerization of the ProDOT parent monomer (3,4-propylenedioxythiophene) in a 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide/propylene carbonate solution at the PNES-SWNT-modified electrode. The electrochemical properties of PProDOT and PProDOT/PNES/SWNT single electrodes and devices were examined using cyclic voltammetric methods. The hybrid composites were found to enhance key supercapacitor figures of merit (charge capacity and capacitance) by approximately a factor of 2 relative to those determined for benchmark Type I devices that exploited a classic PProDOT-based electrode material. The charge/discharge stability of the supercapacitors was probed by repeated rounds of cyclic voltammetric evaluation at a minimum depth of discharge of 73%; these experiments demonstrated that the hybrid PProDOT/PNES/SWNT composites retained ~90% of their initial charge capacity after 21,000 charge/discharge cycles, contrasting analogous data obtained for PProDOT-based devices, which showed only 84% retention of their initial charge capacity.     

Synthesis and characterization of metallic nanoparticles and their incorporation into electroconductive polymer composites

Gold and copper–gold nanoparticles were synthesized using anionic microemulsions as reducing reactors. The microemulsions were prepared using sodium bis(2-ethylhexyl)sulfosuccinate (Aerosol OT) and copper(II) bis(2-ethylhexyl)sulfosuccinate (Cu(AOT)₂) as surfactants, which were dissolved in isooctane containing an appropriate quantity of water. The growth of nanoparticles was monitored by UV/vis spectroscopy and the nanoparticles formed were characterized by transmission electron microscopy (TEM). The metallic nanoparticles were incorporated into films of an electroconductive polymer (ECP) composite: polyaniline-poly(n-butyl methacrylate) (PANI/PBMA) by the casting technique. The nanoparticle-ECP composite films were characterized by scanning electron microscopy (SEM), electrical conductivity measurements and NH₄OH and H₂O₂-sensing capability experiments. The inclusion of nanoparticles results in a cooperative phenomena between the polyaniline and the nanoparticles and as a consequence, the gold nanoparticles increased the electrical conductivity of the ECP film by two orders of magnitude.     

Highly Selective Dispersion of Carbon Nanotubes by Using Poly(phenyleneethynylene)‐Guided Supermolecular Assembly

Isolation of single‐walled carbon nanotubes (SWNTs) with specific chirality and diameters is critical for achieving optimum performance of SWNTs in various applications. A water‐soluble π‐conjugated polymer, poly[(m‐phenyleneethynylene)‐alt‐(p‐phenyleneethynylene)], 3 , is found to exhibit high selectivity in dispersing SWNT (6,5). The polymer's ability to sort out SWNT (6,5) appears to be related to the carbon–carbon triple bond, whose free rotation allows a unique assembly of chromophores in a helical conformation. The observation is consistently supported by fluorescence, Raman, and UV‐vis‐NIR absorption spectra. The intriguing selectivity of 3 to SWNT (6,5), however, is not observed for the vinylene analogue polymer 1 , showing that the carbon–carbon triple bond could play a unique role in sorting out a specific SWNT. The observed selectivity from 3 could be attributed to a combination of the helical cavity size restrain and electronic interaction associated with the local chromophore arrangement. This strategy could be expanded for efficient SWNT sorting when the helical conformation is further finely tuned.     

Structural and electronic properties of Ti-nanowires/C-single wall nanotubes composites by density functional theory calculations

Structural and electronic properties of composite Ti-nanowires/single wall carbon nanotubes ((6,0) and (10,0)) (SWNT) were evaluated by means of density functional theory computations. We considered the cases of monoatomic (MNW), BCC (β-NW) and HCP (α-NW) nanowires that were either inserted or deposited in/on the SWNTs. In all cases the NWs turn the cylindrical SWNTs’ shape to ellipsoid, an effect that is closely related to charge transfer from Ti toward C neighboring atoms. We found that the wires inside the SWNT appear to be more stable compared to the outside cases, while all NWs contribute with new energy states at the Fermi level, transforming the semiconducting (10,0) to a conducting composite. In addition, we found spin up–down differences in the β-NW_on case and electronic charge redistributions e.g. in α-NW_in (charge accumulation internally along the tube's axis) or in α-NW_on (superficial charge accumulation in the vicinity of the NW), accompanied by manifestation of electric dipole moment that reaches the value of 10 Debye in a-NW_on. These results may be of use in the design of new C-based nanocomposite systems suitable for applications in microelectronics, sensors and catalysis.     

Preparation polystyrene/multiwalled carbon nanotubes nanocomposites by copolymerization of styrene and styryl-functionalized multiwalled carbon nanotubes

Styryl-functionalized multiwalled carbon nanotubes (p-MWNTs) were prepared by esterification based on the carboxylate salt of carbon nanotubes and p-chloromethylstyrene in toluene. Then in situ radical copolymerization of p-MWNTs and styrene initiated by 2,2′-azobis(isobutyronitrile) (AIBN) was applied to synthesize composites of styryl-functionalized multiwalled carbon nanotubes and polystyrene (PS) (p-MWNTs/PS). Characterizations carried out by FT-IR, ¹H NMR, UV–vis show that styryl group covalently bond to the surface of MWNTs. The results of UV showed that the solutions of p-MWNTs/PS in chloroform have the hyperchromic effect. Transmission electron microscopy (TEM) images of p-MWNTs/PS composites and scanning electron microscopy (SEM) images of fracture surface of p-MWNTs/PS composites showed the functionalized nanotubes had a better dispersion than that of the unfunctionalized MWNTs in the matrix. The results of thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) suggested that the thermal stability of p-MWNTs/PS composites improved in the presence of MWNTs.     

Anisotropic properties of aligned SWNT modified poly (methyl methacrylate) nanocomposites

The poly (methyl methacrylate) (PMMA)/single-walled carbon nanotube (SWNT) composites with good uniformity, dispersion and alignment of SWNT were fabricated in an improved figuration process. The semidried mixture was stretched along one direction at a drawing ratio of 50 before it was dried, and then folded along the same direction stretching repeatedly for 100 times. The transmission electron microscopic (TEM) observation demonstrated that SWNT in the PMMA/SWNT composite tends to align in the stretching direction owing to a torque exerting on it in the stretching process. The electrical and mechanical properties of PMMA/SWNT composite were studied as a function of SWNT orientation and concentration. The aligned SWNT modified PMMA/SWNT composite presented highly anisotropic properties. The experimental results showed that the electrical conductivity and mechanical properties of composite rise with the increase of SWNT concentration, and that composite films showed higher conductivity and higher mechanical draw ratios along the stretched direction than perpendicular to it. The thermogravimetric analysis (TGA) revealed that embedding the SWNTs into the PMMA matrix also improves the thermal stability of the composite.     

Electrochemical co-deposition and characterization of MnO2/SWNT composite for supercapacitor application

Manganese oxide/single-wall carbon nanotubes (MnO₂/SWNT) composite was co-deposited by the potentiostatic method on a graphite slice. Morphological and structural performances for MnO₂/SWNT composite were characterized by means of scanning electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The wall surface of SWNT was wrapped by ramsdellite MnO₂ nanoparticles to fabricate MnO₂/SWNT coaxial nanotubes, which further interconnected other MnO₂ particles to form the porous MnO₂/SWNT composite. The electrochemical properties were examined by cyclic voltammograms, galvanostatic charge and discharge and electrochemical impedance spectrum. A high specific capacitance of 421 F g^?1 was obtained for overall MnO₂/SWNT composite electrode at the constant current density of 1 A g^?1 in 3 mol L^?1 KCl solution.     

Supramolecular architectures in layer-by-layer films of single-walled carbon nanotubes,chitosan and cobalt (II) phthalocyanine

The building of supramolecular structures in nanostructured films has been exploited for a number of applications, with the film properties being controlled at the molecular level. In this study, we report on the layer-by-layer (LbL) films combining cobalt (II) tetrasulfonated phthalocyanine (CoTsPc), chitosan (Chit) and single-walled carbon nanotubes (SWCNTs) in two architectures, {Chit/CoTsPc}_n and {Chit-SWCNTs/CoTsPc}_n (n = 1–10). The physicochemical properties of the films were evaluated and the multilayer formation was monitored with microgravimetry measurements using a quartz microbalance crystal and an electrochemical technique. According to atomic force microscopy (AFM) results, the incorporation of SWCNTs caused the films to be thicker, with a thickness ca. 3 fold that of a 2-bilayer LbL film with no SWCNTs. Cyclic voltammetry revealed a quasi-reversible, one electron process with E_1/2 at −0.65 V (vs SCE) and an irreversible oxidation process at 0.80 V in a physiological medium for both systems, which can be attributed to [CoTsPc(I)]⁵⁻/[CoTsPc(II)]⁴⁻ and CoTsPc(II) to CoTsPc(III), respectively. The {Chit-SWCNTs/CoTsPc}₅ multilayer film exhibited an increased faradaic current, probably associated with the supramolecular charge transfer interaction between cobalt phthalocyanine and SWCNTs. The results demonstrate that an intimate contact at the supramolecular level between functional SWCNTs immobilized into biocompatible chitosan polymer and CoTsPc improves the electron flow from CoTsPc redox sites to the electrode surface.     

Charge Transfer at Junctions of a Single Layer of Graphene and a Metallic Single Walled Carbon Nanotube

Junctions between a single walled carbon nanotube (SWNT) and a monolayer of graphene are fabricated and studied for the first time. A single layer graphene (SLG) sheet grown by chemical vapor deposition (CVD) is transferred onto a SiO₂/Si wafer with aligned CVD‐grown SWNTs. Raman spectroscopy is used to identify metallic‐SWNT/SLG junctions, and a method for spectroscopic deconvolution of the overlapping G peaks of the SWNT and the SLG is reported, making use of the polarization dependence of the SWNT. A comparison of the Raman peak positions and intensities of the individual SWNT and graphene to those of the SWNT‐graphene junction indicates an electron transfer of 1.12 × 10¹³ cm^?2 from the SWNT to the graphene. This direction of charge transfer is in agreement with the work functions of the SWNT and graphene. The compression of the SWNT by the graphene increases the broadening of the radial breathing mode (RBM) peak from 3.6 ± 0.3 to 4.6 ± 0.5 cm^?1 and of the G peak from 13 ± 1 to 18 ± 1 cm^?1, in reasonable agreement with molecular dynamics simulations. However, the RBM and G peak position shifts are primarily due to charge transfer with minimal contributions from strain. With this method, the ability to dope graphene with nanometer resolution is demonstrated.     

Odako growth of dense arrays of single-walled carbon nanotubes attached to carbon surfaces

A novel process is demonstrated whereby dense arrays of single-walled carbon nanotubes (SWNT) are grown directly at the interface of a carbon material or carbon fiber. This growth process combines the concepts of SWNT tip growth and alumina-supported SWNT base growth to yield what we refer to as “odako” growth. In odako growth, an alumina flake detaches from the carbon surface and supports catalytic growth of dense SWNT arrays at the tip, leaving a direct interface between the carbon surface and the dense SWNT arrays. In addition to being a new and novel form of SWNT array growth, this technique provides a route toward future development of many important applications for dense aligned SWNT arrays. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users. This article is published with open access at Springerlink.com     

Integration of carbon nanotubes as hole transport electrode in polymer/fullerene bulk heterojunction solar cells

Transparent and conductive single-walled carbon nanotube (SWNT) thin films were fabricated onto glass substrates and their optical and electrical properties were evaluated. Particular attention was given to the dependence of the conductivity and optical transparency on the thickness of the films. Furthermore, the SWNT thin films were integrated in organic photovoltaic devices as the hole transport electrode. The best photovoltaic performance was observed for the devices utilizing 80 nm SWNT films with a sheet resistance of 362 Ω/sq, and a transmittance of 64% at 520 nm. The experiments reveal that SWNTs films can be used as transparent electrodes for efficient, flexible organic photovoltaic devices.     

Functionalization of single- and multi-walled carbon nanotubes with cationic amphiphiles for plasmid DNA complexation and transfection

The possibility of delivering DNA efficiently to cells represents a crucial issue for the treatment of both genetic and acquired diseases. However, even although the efficiency of non-viral transfection systems has improved in the last decade, none have yet proven to be sufficiently effective in vivo. We report herein our results on the functionalization of single-walled carbon nanotubes (SWNT) and multi-walled carbon nanotubes (MWNT) by two cationic amphiphiles (lipid RPR120535 and pyrenyl polyamine), their use for the complexation of plasmid DNA, and their efficiency in transfecting cells in vitro. The experiments have shown that the efficiency of transfection is higher when using SWNT instead of MWNT, and that transfection efficiency is similar or slightly higher when using nanoplexes (SWNT/lipid RPR120535/DNA) instead of lipoplexes (lipid RPR120535/DNA) and several orders of magnitude higher than that of naked DNA. This study therefore shows both that the transfection is better when using SWNTs and that it is dependent on the nature of the amphiphilic molecules adsorbed on the nanotubes.