Transparent conductive thin film synthesis based on single-walled carbon nanotubes dispersion containing polymethylmethacrylate binder

Transparent conductive hybrid thin films of single-walled carbon nanotubes (SWNTs) and polymethyl methacrylate (PMMA) are fabricated using dispersions containing SWNTs and water-borne PMMA binder. The polymer binder was used as adhesion promoter between the SWNTs and the substrate. The polymer binder content in the SWNTs dispersion is varied to obtain the optimum optical transmittance, electrical conductivity, and mechanical adhesion. The PMMA and SWNT network formed the composite over substrate. The fabricated SWNTs/PMMA hybrid films are immersed in nitric acid (HNO3) and thionyl chloride (SOCl2) to improve electrical conductivity. SWNTs films with 0.2-0.6 mg/ml polymer binder have sheet resistance of 80-140 ohms/sq at a transmittance of about 80% and a strong adhesion on glass substrate. Furthermore, the electrical stability of the films is improved via the PMMA addition. This results indicates that the SWNTs/PMMA hybrid films fabricated by this method can be used as an alternative of indium tin oxide (ITO) film on flexible substrate.     

Fluorescent Polymer—Single‐Walled Carbon Nanotube Complexes with Charged and Noncharged Dendronized Perylene Bisimides for Bioimaging Studies

Fluorescent nanomaterials are expected to revolutionize medical diagnostic, imaging, and therapeutic tools due to their superior optical and structural properties. Their inefficient water solubility, cell permeability, biodistribution, and high toxicity, however, limit the full potential of their application. To overcome these obstacles, a water‐soluble, fluorescent, cytocompatible polymer—single‐walled carbon nanotube (SWNT) complex is introduced for bioimaging applications. The supramolecular complex consists of an alkylated polymer conjugated with neutral hydroxylated or charged sulfated dendronized perylene bisimides (PBIs) and SWNTs as a general immobilization platform. The polymer backbone solubilizes the SWNTs, decorates them with fluorescent PBIs, and strongly improves their cytocompatibility by wrapping around the SWNT scaffold. In photophysical measurements and biological in vitro studies, sulfated complexes exhibit superior optical properties, cellular uptake, and intracellular staining over their hydroxylated analogs. A toxicity assay confirms the highly improved cytocompatibility of the polymer‐wrapped SWNTs toward surfactant‐solubilized SWNTs. In microscopy studies the complexes allow for the direct imaging of the SWNTs' cellular uptake via the PBI and SWNT emission using the 1st and 2nd optical window for bioimaging. These findings render the polymer‐SWNT complexes with nanometer size, dual fluorescence, multiple charges, and high cytocompatibility as valuable systems for a broad range of fluorescence bioimaging studies.     

Fluorescence Enhancement on Large Area Self‐Assembled Plasmonic‐3D Photonic Crystals

Discontinuous plasmonic‐3D photonic crystal hybrid structures are fabricated in order to evaluate the coupling effect of surface plasmon resonance and the photonic stop band. The nanostructures are prepared by silver sputtering deposition on top of hydrophobic 3D photonic crystals. The localized surface plasmon resonance of the nanostructure has a symbiotic relationship with the 3D photonic stop band, leading to highly tunable characteristics. Fluorescence enhancements of conjugated polymer and quantum dot based on these hybrid structures are studied. The maximum fluorescence enhancement for the conjugated polymer of poly(5‐methoxy‐2‐(3‐sulfopropoxy)‐1,4‐phenylenevinylene) potassium salt by a factor of 87 is achieved as compared with that on a glass substrate due to the enhanced near‐field from the discontinuous plasmonic structures, strong scattering effects from rough metal surface with photonic stop band, and accelerated decay rates from metal‐coupled excited state of the fluorophore. It is demonstrated that the enhancement induced by the hybrid structures has a larger effective distance (optimum thickness ≈130 nm) than conventional plasmonic systems. It is expected that this approach has tremendous potential in the field of sensors, fluorescence‐imaging, and optoelectronic applications.     

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.     

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.     

Light sensing in a photoresponsive, organic-based complementary inverter

A photoresponsive organic complementary inverter was fabricated and its light sensing characteristics was studied. An organic circuit was fabricated by integrating p-channel pentacene and n-channel copper hexadecafluorophthalocyanine (F16CuPc) organic thin-film transistors (OTFTs) with a polymeric gate dielectric. The F16CuPc OTFT showed typical n-type characteristics and a strong photoresponse under illumination. Whereas under illumination, the pentacene OTFT showed a relatively weak photoresponse with typical p-type characteristics. The characteristics of the organic electro-optical circuit could be controlled by the incident light intensity, a gate bias, or both. The logic threshold (V(M), when V(IN) = V(OUT)) was reduced from 28.6 V without illumination to 19.9 V at 6.94 mW/cm2. By using solely optical or a combination of optical and electrical pulse signals, light sensing was demonstrated in this type of organic circuit, suggesting that the circuit can be potentially used in various optoelectronic applications, including optical sensors, photodetectors and electro-optical transceivers.     

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.     

On‐Chip Chemical Self‐Assembly of Semiconducting Single‐Walled Carbon Nanotubes (SWNTs): Toward Robust and Scale Invariant SWNTs Transistors

In this paper, the fabrication of carbon nanotubes field effect transistors by chemical self‐assembly of semiconducting single walled carbon nanotubes (s‐SWNTs) on prepatterned substrates is demonstrated. Polyfluorenes derivatives have been demonstrated to be effective in selecting s‐SWNTs from raw mixtures. In this work the authors functionalized the polymer with side chains containing thiols, to obtain chemical self‐assembly of the selected s‐SWNTs on substrates with prepatterned gold electrodes. The authors show that the full side functionalization of the conjugated polymer with thiol groups partially disrupts the s‐SWNTs selection, with the presence of metallic tubes in the dispersion. However, the authors determine that the selectivity can be recovered either by tuning the number of thiol groups in the polymer, or by modulating the polymer/SWNTs proportions. As demonstrated by optical and electrical measurements, the polymer containing 2.5% of thiol groups gives the best s‐SWNT purity. Field‐effect transistors with various channel lengths, using networks of SWNTs and individual tubes, are fabricated by direct chemical self‐assembly of the SWNTs/thiolated‐polyfluorenes on substrates with lithographically defined electrodes. The network devices show superior performance (mobility up to 24 cm² V^?1 s^?1), while SWNTs devices based on individual tubes show an unprecedented (100%) yield for working devices. Importantly, the SWNTs assembled by mean of the thiol groups are stably anchored to the substrate and are resistant to external perturbation as sonication in organic solvents.     

Amperometric biosensors based on redox polymer-carbon nanotube-enzyme composites

Based on their size and unique electrical properties, carbon nanotubes offer the exciting possibility of developing ultrasensitive, electrochemical biosensors. In this study, we describe the construction of amperometric biosensors based on the incorporation of single-walled carbon nanotubes modified with enzyme into redox polymer hydrogels. The composite films were constructed by first incubating an enzyme in a single-walled carbon nanotube (SWNTs) solution and then cross-linking within a poly[(vinylpyridine)Os(bipyridyl)(2)Cl(2+/3+)] polymer film. Incorporation of SWNTs, modified with glucose oxidase, into the redox polymer films resulted in a 2-10-fold increase in the oxidation and reduction peak currents during cyclic voltammetry, while the glucose electrooxidation current was increased 3-fold to approximately 1 mA/cm(2) for glucose sensors. Similar effects were also observed when SWNTs were modified with horseradish peroxidase prior to incorporation into redox hydrogels.     

In situ synthesis and optical limiting response of poly(N-vinylcarbazole) functionalized single-walled carbon nanotubes

A new poly(N-vinylcarbazole)-covalently grafted single-wall carbon nanotube (SWNT-PVK) hybrid material was synthesized by an in situ anionic polymerization reaction of N-vinylcarbazole and the negatively charged SWNTs. Incorporation of the PVK moieties onto the SWNTs' surface considerably improves the solubility and processability of SWNTs. At the same level of linear transmission, the SWNT-PVK dispersions show better optical limiting performance than the pristine SWNT dispersions, which shows this material to be a suitable candidate for viable optical limiting devices. Micro-plasma and/or micro-bubble induced nonlinear scattering is considered as the main mechanism for optical limiting.     

Preparation,solubility, and electrorheological properties of carbon nanotubes/poly(methyl methacrylate) nanocomposites by in situ functionalization

Poly(methyl methacrylate) (PMMA) nanobeads-decorated multi-walled carbon nanotubes (MWNTs) and single-walled carbon nanotubes (SWNTs) nanocomposites were prepared using two processing steps. Initially, spherical PMMA nanoparticles were synthesized using an emulsion polymerization method. Afterward, the PMMA nanobeads were decorated to MWNTs and SWNTs using benzoyl peroxide as an initiator in water during a high temperature refluxing process. The results confirmed the linkage of the nanotubes to the surrounding PMMA nanobeads via a covalent bond. The resultant nanocomposites showed high solubility in chloroform without flocculation after 24 h. In addition, the nanotubes/PMMA nanocomposites were characterized by electrical resistance measurements to analyze their electrical conductivity and examined as electrorheological (ER) materials when dispersed in silicone oil.     

Aggregation behavior of chemically attached poly(ethylene glycol) to single-walled carbon nanotubes (SWNTs) ropes

The aggregation behavior of poly(ethylene glycol) (PEG)-grafted single-walled carbon nanotubes (SWNTs) was investigated by Fourier transform infrared (FTIR), thermogravimetric analysis (TGA), and high-resolution transmission electron microscopy (HR-TEM). The hybrid functional material was synthesized by producing carboxylic acid groups at nanotube ends and side-wall defect sites, which provide reaction sites for various guest species, followed by a reaction with hydroxyl-terminated PEG in various solvents. FTIR and TGA analyses confirm that the PEG chains were covalently attached to the functionalized SWNTs ropes. Transmission electron microscopy (TEM) images of the PEG-grafted SWNTs revealed two different morphologies, depending on solvent quality: PEG and SWNT segments self-organize into ring-like structure in which the aggregated PEG core is surrounded by SWNT bundles, when freshly prepared PEG-grafted SWNTs are cast from benzene/tetrahydrofuran solvent mixture. Instead, the hybrid polymers form a highly dispersed morphology in selective solvents for SWNTs. The novel aggregation mode originates from strong association of polymer chains with nanotubes, as in the aggregation behavior of micro-phase separated copolymers in dilute solution.     

Novel photoactive fluorene-based terpolymers incorporating carbazole for photovoltaic application

A series of novel photoactive conjugated terpolymers based on N-alkyl carbazole, 9,9-didecylfluorene, and bis(thienyl)benzothiadiazole were synthesized by the Pd-catalyzed Suzuki polymerization method with various molar ratios of the carbazole derivatives. Electron-deficient benzothiadiazole and electron-rich carbazole moieties were incorporated into the polymer backbone to obtain the broad absorption spectrum and to improve the hole-transporting characteristics, respectively. The polymer solar cell (PSC) was fabricated with a layered structure of ITO/PEDOT: PSS/polymer:C71-PCBM (1:3)/LiF/Al. The best performance of PSC was obtained at P1:C71-PCBM whose reaches a power conversion efficiency (PCE) of 2.62%, with a short circuit current density (J(SC)) of 8.61 mA/cm2, an open circuit voltage (V(OC)) of 0.82 V, and a fill factor (FF) of 0.37 under AM 1.5 G irradiation (100 mW/cm2).     

Cover Picture: Novel Photoactive Single‐Walled Carbon Nanotube–Porphyrin Polymer Wraps: Efficient and Long‐Lived Intracomplex Charge Separation (Adv. Mater. 7/2005)

The figure on the cover portrays a novel donor–acceptor nanoassembly, based on a single‐walled carbon nanotube (SWNT) as the electron acceptor and poly(methyl methacrylate) (PMMA)‐carrying porphyrin units (H2P) as the excited‐state electron donors. In these supramolecular “polymer wraps”, reported on p. 871 by Guldi and co‐workers, SWNTs quench the photoexcited H2P chromophores, resulting in the creation of microsecond‐lived radical ion pairs.     

The evaluation of individual dispersion of single-walled carbon nanotubes using absorption and fluorescence spectroscopic techniques

We have investigated the degree of dispersion of single-walled carbon nanotubes (SWNTs) in solution using laser spectroscopic techniques. SWNTs were suspended in aqueous media using a sodium dodecyl sulfate (SDS) surfactant. SWNTs with different dispersion states were prepared by controlling the intensity and duration of sonication and centrifugation. The absorption and fluorescence spectroscopic techniques were employed to characterize the different dispersion state of the prepared samples. Nanotube suspensions with better dispersion showed higher fluorescence and sharper absorption peaks. The fluorescence data were characterized as a function of the nanotube chirality, and absorption peak shifts were analyzed depending on the first and second van Hove singularities (vHs) of semiconducting nanotubes.     

High-performance electronics using dense, perfectly aligned arrays of single-walled carbon nanotubes

Single-walled carbon nanotubes (SWNTs) have many exceptional electronic properties. Realizing the full potential of SWNTs in realistic electronic systems requires a scalable approach to device and circuit integration. We report the use of dense, perfectly aligned arrays of long, perfectly linear SWNTs as an effective thin-film semiconductor suitable for integration into transistors and other classes of electronic devices. The large number of SWNTs enable excellent device-level performance characteristics and good device-to-device uniformity, even with SWNTs that are electronically heterogeneous. Measurements on p- and n-channel transistors that involve as many as approximately 2,100 SWNTs reveal device-level mobilities and scaled transconductances approaching approximately 1,000 cm(2) V(-1) s(-1) and approximately 3,000 S m(-1), respectively, and with current outputs of up to approximately 1 A in devices that use interdigitated electrodes. PMOS and CMOS logic gates and mechanically flexible transistors on plastic provide examples of devices that can be formed with this approach. Collectively, these results may represent a route to large-scale integrated nanotube electronics.     

In situ polymerization of acetylene polymer on single-walled carbon nanotube and its application to photoinduced charge transfer system

An acetylene polymer is formed on single-walled carbon nanotubes (SWNTs) using in situ polymerization. The acetylene polymers/SWNTs composite is hydrophilic even water-soluble, and has a structure of donor/acceptor dyad. In measurements of photocurrents-voltage curves, the composite film exhibits a power conversion efficiency of 1.50 x 10(-2%) under illumination (I = 80 mW/cm2, air mass 1.5 condition).     

Electrochemical and optical properties of a new donor–acceptor type conjugated polymer derived from 3,4–didodecyloxythiophene

In this communication, we report the synthesis and characterization of a new donor–acceptor type conjugated polymer carrying alternate 3,4-didodecyloxythiophene and (1,3,4-oxadiazol-yl)pyridine moieties and evaluation of its optical and electrochemical properties. The polymer was synthesized through precursor polyhydrazide route. It has well defined structure, stability and it shows good solubility in common organic solvents. Optical and electrochemical properties were studied by UV-visible, fluorescence spectroscopy and cyclic voltammetric studies, respectively. It displays bluish-green fluorescence both in solution and in film state. Cyclic voltammetric studies showed that the polymer P1 possesses a HOMO energy level of −6·01 and LUMO energy level of −3·34 eV. The preliminary studies clearly reveal that the new polymer can have potential application in the fabrication of light emitting diodes. The studies on its device application are in progress.     

Synthesis of a new conjugated polymer composed of pyrene and bithiophene units for organic solar cells

An alternating conjugated copolymer composed of pyrene and bithiophene units, poly(DHBT-alt-PYR) has been synthesized. The synthesized polymer was found to exhibit good solution processibility and thermal stability, losing less than 5% of their weight on heating to approximately 370 degrees C. The synthesized polymer showed its maximum absorption and peak PL emission at 401 and 548 nm, respectively. The optical band gap energy of the polymer was determined by absorption onset to be 2.64 eV. Highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of the polymer was determined to be -5.48 and -2.84 eV by cyclic voltametry (CV) and the optical band gap. The polymer photovoltaic devices were fabricated with a typical sandwich structure of ITO/PEDOT:PSS/active layer/LiF/Al using poly(DHBT-alt-PYR) as an electron donor and C60-PCBM or C70-PCBM as electron acceptors. The open circuit voltage, short circuit current and fill factor of the device using C70-PCBM as an acceptor were 0.75 V, 3.80 mA/cm2 and 0.28, respectively, and the maximum power conversion efficiency of the device was 0.80%.     

Measurement of effective piezoelectric coefficients of PZT thin films for energy harvesting application with interdigitated electrodes

Interdigitated electrode (IDE) systems with lead zirconate titanate (PZT) thin films play an increasingly important role for two reasons: first, such a configuration generates higher voltages than parallel plate capacitor-type electrode (PPE) structures, and second, the application of an electric field leads to a compressive stress component in addition to the overall stress state, unlike a PPE structure, which results in tensile stress component. Because ceramics tend to crack at relatively moderate tensile stresses, this means that IDEs have a lower risk of cracking than PPEs. For these reasons, IDE systems are ideal for energy harvesting of vibration energy, and for actuators. Systematic investigations of PZT films with IDE systems have not yet been undertaken. In this work, we present results on the evaluation of the in-plane piezoelectric coefficients with IDE systems. Additionally, we also propose a simple and measurable figure of merit (FOM) to analyze and evaluate the relevant piezoelectric parameter for harvesting efficiency without the need to fabricate the energy harvesting device. Idealized effective coefficients e(IDE) and h(IDE) are derived, showing its composite nature with about one-third contribution of the transverse effect, and about two-thirds contribution of the longitudinal effect in the case of a PZT film deposited on a (100)-oriented silicon wafer with the in-plane electric field along one of the <011> Si directions. Randomly oriented 1-μm-thick PZT 53/47 film deposited by a sol-gel technique, was evaluated and yielded an effective coefficient e(IDE) of 15 C???m(???2). Our FOM is the product between effective e and h coefficient representing twice the electrical energy density stored in the piezoelectric film per unit strain deformation (both for IDE and PPE systems). Assuming homogeneous fields between the fingers, and neglecting the contribution from below the electrode fingers, the FOM for IDE structures with larger electrode gap is derived to be twice as large as for PPE structures, for PZT-5H properties. The experiments yielded an FOM of the IDE structures of 1.25 × 10(10) J/m(3) and 14 mV/μ strain.