Near-infrared photoresponse in single-walled carbon nanotube/polymer composite films

We present a near-infrared photoresponse study of single-walled carbon nanotube/poly(3-hexylthiophene)-block-polystyrene polymer (SWCNT/P3HT-b-PS) composite films for different loading ratios of SWCNT in the polymer matrix. Compared to the pure SWCNT film, the photoresponse [(light current − dark current)/dark current] is much larger in the SWCNT/polymer composite films. The photoresponse is up to 157% when SWCNTs are embedded in P3HT-b-PS while for a pure SWCNT film it is only 40%. We also show that the photocurrent strongly depends on the position of the laser spot with maximum photocurrent occurring at the metal-film interface. We explain the photoresponse due to exciton dissociations and charge carrier separation caused by a Schottky barrier at the metallic electrode-SWCNT interface.     

Poly(l-lactide)/nano-structured carbon composites: Conductivity, thermal properties, crystallization, and biodegradation

The effects of nano-structured carbon fillers [fullerene C₆₀, single wall carbon nanotube (SWCNT), carbon nanohorn (CNH), carbon nanoballoon (CNB), and ketjenblack (KB)] and conventional carbon fillers [conductive grade and graphitized carbon black (CB)] on conductivity (resistance), thermal properties, crystallization, and proteinase K-catalyzed enzymatic degradation of poly(l-lactide) [i.e., poly(l-lactic acid) (PLLA)] films were investigated. Even at low filler concentrations such as 1 wt%, the addition of SWCNT effectively decreased the resistivity of PLLA film compared with that of conventional CB, and PLLA-SWCNT film with filler concentration of 10 wt% attained the resistivity lower than 100 Ω cm. The crystallization of PLLA further decreased the resistivity of films. The addition of carbon fillers, except for C₆₀ and CNB at 5 wt%, lowered the glass transition temperature, whereas the addition of carbon fillers, excluding C₆₀, elevated softening temperatures, if an appropriate filler concentration was selected. On heating from room temperature, cold crystallization temperature was determined mainly by the molecular weight of PLLA, whereas on cooling from the melt, the carbon fillers, excluding KB, elevated the cold crystallization temperature, reflecting the effectiveness of most of the carbon fillers as nucleating agents. Despite the nucleating effects, the addition of carbon fillers decreased the enthalpy of cold crystallization of PLLA on both heating and cooling. The addition of CNH, CNB, and CB elevated the starting temperature of thermal degradation of PLLA, whereas the addition of SWCNT reduced the thermal stability. Furthermore, the addition of C₆₀ and SWCNT enhanced the enzymatic degradation of PLLA, whereas the addition of KB and CNB disturbed the enzymatic degradation of PLLA. The reasons for the effects of carbon fillers on the physical properties, crystallization, and enzymatic degradation of PLLA films are discussed.     

A significant improvement of both yield and purity during SWCNT synthesis via the electric arc process

This paper deals with the optimisation of the single walled carbon nanotube (SWCNT) synthesis by the electric arc technique using so-called heterogeneous anodes filled with Ni and Y catalysts along with either graphite (large-grain or small-grain) or diamond powders. The various carbon nanophases produced were analyzed using high-resolution transmission electron microscopy. Plasma physical properties were determined by emission spectroscopy and were correlated to the variation in the carbon products formed. Using large-grain (100 μm) graphite powder corresponded to standard conditions since able to generate impurity-rich SWCNT material resembling that usually described in literature. However, replacing the large-grain graphite powder by small-grain graphite powder (∼1 μm) resulted in a dramatic increase in both the yield and purity of the SWCNTs obtained. On the other hand, a similar result was obtained by using diamond powder (grain size ∼1 μm) instead of the small-grain graphite powder. The results are explained via the erosion modes of the anodes with respect to the apparent density of the powder mixtures filling their cavities. Maintaining a steady plasma composition and a CI/NiI concentration ratio higher than 10⁸ are identified as two conditions required for optimising SWCNT synthesis.     

PAN/SAN/SWNT ternary composite: Pore size control and electrochemical supercapacitor behavior

Single wall carbon nanotubes (SWNT) act as a compatabilizer for polyacrylonitrile (PAN)/styrene-acrylonitrile (SAN) copolymer blends. Carbonization of PAN/SAN/SWNT blend films results in pore widths in the range of 1-200 nm, while carbonized PAN/SAN blend films resulted in pores with typical width of 1-10 μm. Electrochemical supercapacitor behavior of the carbonized PAN/SAN/SWNT films was characterized using 6 M KOH electrolyte. Surface area and pore size distribution were analyzed using nitrogen gas adsorption and the BET and DFT theories. Double layer capacity of the carbonized PAN/SAN/SWNT films was as high as 205 μF/cm² based on the BET surface area.     

Synthesis, characterization and the electrocatalytic behaviour of nickel (II) tetraamino-phthalocyanine chemically linked to single walled carbon nanotubes

In this work we report on the synthesis, characterization and the electrochemical behavior of amide linked nickel (II) tetraamino-phthalocyanine (NiTAPc)-single walled carbon nanotube (SWCNT) nanomaterials (NiTAPc-SWCNT (linked)). UV-vis, XRD, IR and Raman spectroscopies were used in characterization whilst cyclic voltammetry was used to study the electrochemical behavior of NiTAPc-SWCNT (linked)-GCE. Relative to the bare glassy carbon electrode (bare-GCE), SWCNT-GCE, NiTAPc-GCE, and NiTAPc/SWCNT (mixed)-GCE, the NiTAPc-SWCNT (linked)-GCE gave the best current responses for the oxidation of 2-mercaptoethanol (2-ME). The catalytic rate constant is of the magnitude of 10³ M⁻¹ s⁻¹ while the detection limit (LOD) is 0.15 μM using the 3δ notation, with a sensitivity of 2.53 μA μM⁻¹ cm⁻².     

Synthesis of double-walled carbon nanotube films and their field emission properties

Continuous double-walled carbon nanotube (DWCNT) films were synthesized using an Fe-Mo catalyst by the arc discharge method. This new catalyst has dramatically improved the purity and selectivity of DWCNT product. High-resolution transmission electron microscopy indicates that the outer and inner diameter of DWCNT are 1.9-4.7 nm and 1.2-3.8 nm, respectively. The field emission properties of DWCNT films have been studied. The directly grown film was transferred onto quartz substrates and used as emission cathodes, and has demonstrated a quite good emission performance. Moreover, the emissions of DWCNT films have been further improved by heat treatment. The film after 400 °C oxidation shows excellent field emission property with a low turn-on (E_to = 0.6 V/μm) and threshold field (E_th = 0.9 V/μm) corresponding to the emission current density of 1 μA/cm² and 1 mA/cm², respectively.     

Cathodoluminescence and electron field emission of boron-doped a-C:N films

The optical and electrical properties of so-called carbon nitride films (a-C:N) and boron doped so-called carbon nitride films (a-C:N:B) are studied with cathodoluminescence (CL) spectroscopy and electron field emission measurement. The a-C:N films were first deposited on Si by a filtered cathodic arc plasma system, and then boron ions (∼1 × 10¹⁶ cm⁻²) were implanted into the a-C:N films to form a-C:N:B films by a medium current implanter. The structural and morphological properties of a-C:N and a-C:N:B films were then analyzed using secondary ion mass spectrometer, X-ray photoelectron spectroscopy, FT-IR spectra, Raman spectroscopy and atomic force microscopy. The a-C:N film exhibits luminescence of blue light (∼2.67 eV) and red light (∼1.91 eV), and the a-C:N:B film displays luminescence of blue light (∼2.67 eV) in CL spectra measured at 300 K. Furthermore, the incorporated boron atoms change the electron field emission property, which shows a higher turn on field for the a-C:N:B film (3.6 V/μm) than that for the a-C:N film (2.8 V/μm).     

A chemically amplified positive-working photosensitive polyimide based on a blend of poly(amic acid ethoxymethyl ester) and poly(amic acid)

We prepared a novel chemically amplified photosensitive polyimide based on a blend of poly(amic acid ethoxymethyl ester) (PAAE) and poly(amic acid); this blend produces polyimide (PI) films with improved mechanical properties after imidization with photoacid generator (PAG). PAAE and poly(amic acid) were end-capped with 5-norbornene-2,3-dicarboxylic dianhydride and 2,3-dimethyl maleic anhydride, respectively, to lower their molecular weights without compromising the properties of the resulting PI films. As a result of the blending of these PI precursors, the mechanical properties of the PI films were found to be less affected by the strong acid generated from the PAG than PI films fabricated by imidization of PAAE alone. The relatively high solubility of the blended PI precursor film in basic aqueous solutions was found to be effectively controlled by the use of a high-temperature post-exposure bake process to partially imidize the end-capped PAA. It was found that a 10-μm-thick film of the PSPI precursor system containing 13 wt% PAGs exhibits a sensitivity (D⁰) of 700 mJ/cm² when developed with 2.38 wt% aqueous tetramethyl ammonium hydroxide solution at room temperature. A fine positive pattern was fabricated in a 12 μm thick film with 1000 mJ/cm² of i-line exposure. The resultant PI film was also found to exhibit excellent mechanical and thermal properties, which are critical to its practical use as a stress buffer layer in semiconductor packaging.     

Towards the conception of an amperometric sensor of l-tyrosine based on Hemin/PAMAM/MWCNT modified glassy carbon electrode

A novel amperometric sensor was fabricated based on the immobilization of hemin onto the poly (amidoamine)/multi-walled carbon nanotube (PAMAM/MWCNT) nanocomposite film modified glassy carbon electrode (GCE). Electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and ultraviolet visible (UV-vis) adsorption spectroscopy were used to investigate the possible state and electrochemical activity of the immobilized hemin. In the Hemin/PAMAM/MWCNT nanocomposite film, MWCNT layer possessed excellent inherent conductivity to enhance the electron transfer rate, while the layer of PAMAM greatly enlarged the surface average concentration of hemin (Γ) on the modified electrode. Therefore, the nanocomposite film showed enhanced electrocatalytical activity towards the oxidation of l-tyrosine. The kinetic parameters of the modified electrode were investigated. In pH 7.0 phosphate buffer solution (PBS), the sensor exhibits a wide linear range from 0.1 μM to 28.8 μM l-tyrosine with a detection limit of 0.01 μM and a high sensitivity of 0.31 μA μM⁻¹ cm⁻². In addition, the response time of the l-tyrosine sensor is less than 5 s. The excellent performance of the sensor is largely attributed to the electro-generated high reactive oxoiron (IV) porphyrin (O = Fe^IV-P) which effectively catalyzed the oxidation of l-tyrosine. A mechanism was herein proposed for the catalytic oxidation of l-tyrosine by oxoiron (IV) porphyrin complexes.     

Carbon black thin films with tunable resistance and optical transparency

Layer-by-layer assembly was used to produce highly conductive thin films of carbon black and polymer. Positively and negatively-charged polyelectrolytes, polyethylenimine (PEI) and poly(acrylic acid) (PAA), were used to stabilize carbon black in aqueous mixtures that were then deposited onto a PET substrate. The effects of sonication and pH adjustment of deposition mixtures on the conductivity and transparency of deposited films was studied, along with drying temperature. Sonication and oven drying at 70 °C produced films with the lowest sheet resistance (∼1500 Ω/sq), which is a bulk resistivity below 0.2 Ω cm for a 14-bilayer film that is 1.3 μm thick. These two variables improve packing and connectivity amongst carbon black particles that results in increased electrical conductivity. Increasing the pH of the PAA-stabilized mixture and decreasing the pH of the PEI-stabilized mixture resulted in transparent films due to increased polymer charge density. These pH-adjusted films have much higher sheet resistance values than their non-adjusted counterparts due to their reduced thickness and patchy deposition. Varying the number of bilayers allows both sheet resistance and optical transparency to be tailored over a broad range. Carbon black-filled thin films able to achieve these levels of resistivity and transparency may find application in a variety of optoelectronic applications.     

Nonisothermal crystallization behavior and UV screening ability of poly(ethylene terephthalate)/carbon black transparent films

A UV absorbent was blended with virgin carbon black to prepare modified carbon black (m-CB) using a solid phase modification. The mixed solutions of poly(ethylene terephthalate) (PET)/CB and PET/m-CB were coated on glass substrates to fabricate light screening films. Scanning electron microscopy (SEM) showed that m-CB had better dispersibility than CB in PET matrix. Nonisothermal crystallization kinetics of virgin PET, PET/CB, and PET/m-CB films were investigated by differential scanning calorimetry (DSC). The data were described by a modified Avrami model. The results showed CB and m-CB acted as nucleating agents and increased the crystallization rate of PET. But due to the low crystallization capacity of copolymerized PET (co-PET) matrix, the nucleating effects were not as obvious as expected. The addition of 4 wt% m-CB improved the UV screening ability of the composite film significantly and just slightly increased their haze.     

Structure and properties of polyacrylonitrile/single wall carbon nanotube composite films

Polyacrylonitrile (PAN)/single wall carbon nanotube (SWNT) composite films have been processed with unique combination of tensile strength (103 MPa), modulus (10.9 GPa), electrical conductivity (1.5×10⁴ S/m), dimensional stability (coefficient of thermal expansion 1.7×10⁻⁶/°C), low density (1.08 g/cm³), solvent resistance, and thermal stability. PAN molecular motion above the glass transition temperature (T_g) in the composite film is significantly suppressed, resulting in high PAN/SWNT storage modulus above T_g (40 times the PAN storage modulus). Rope diameter in the SWNT powder was 26 nm, while in 60/40 PAN/SWNT film, the rope diameter was 40 nm. PAN crystallite size from (110) plane in PAN and PAN/SWNT films was 5.3 and 2.9 nm, respectively. This study suggests good interaction between PAN and SWNT.     

Electrochemical characterization of amorphous LiFe(WO4)2 thin films as positive electrodes for rechargeable lithium batteries

Amorphous LiFe(WO₄)₂ thin films have been fabricated by radio-frequency (R.F.) sputtering deposition at room temperature. The as-deposited and electrochemically cycled thin films are, respectively, characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, and X-ray photoelectron spectra techniques. An initial discharge capacity of 198 mAh/g in Li/LiFe(WO₄)₂ cells is obtained, and the electrochemical behavior is mostly preserved in the following cycling. These results identified the electrochemical reactivity of two redox couples, Fe³⁺/Fe²⁺ and W⁶⁺/W^x+ (x = 4 or 5). The kinetic parameters and chemical diffusion coefficients of Li intercalation/deintercalation are estimated by cyclic voltammetry and alternate-current (AC) impedance measurements. All-solid-state thin film lithium batteries with Li/LiPON/LiFe(WO₄)₂ layers are fabricated and show high capacity of 104 μAh/cm² μm in the first discharge. As-deposited LiFe(WO₄)₂ thin film is expected to be a promising positive electrode material for future rechargeable thin film batteries due to its large volumetric rate capacity, low-temperature fabrication and good electrode/electrolyte interface.     

Epoxy-based carbon films with high electrical conductivity attached to an alumina substrate

Carbon-based films (0.8-13 μm thick) with good bonding to the substrate and high processability were produced at 650 °C on an alumina substrate, using SU 2.5 bisphenol-A type novolac epoxy (plus triethyleneteramine curing agent) as the carbon precursor. This precursor gave crack-free and scratch resistant carbon films. Interconnected filamentary nickel nanoparticles were more effective for conductivity enhancement than silver nanoparticles or multiwalled carbon nanotubes at 5 vol.% or below, in spite of the high conductivity of silver and the high aspect ratio of nanotubes. The carbon film with 2.5 vol.% nickel showed resistivity 6 × 10⁻³ Ω cm.     

Improvement of field emission performance on nitrogen ion implanted ultrananocrystalline diamond films through visualization of structure modifications

The relationship between the electron field emission properties and structure of ultra-nanocrystalline diamond (UNCD) films implanted by nitrogen ions or carbon ions was investigated. The electron field emission properties of nitrogen-implanted UNCD films and carbon-implanted UNCD films were pronouncedly improved with respect to those of as-grown UNCD films, that is, the turn-on field decreased from 23.2 V/μm to 12.5 V/μm and the electron field emission current density increased from 10E−5 mA/cm² to 1 × 10E−2 mA/cm². The formation of a graphitic phase in the nitrogen-implanted UNCD films was demonstrated by Raman microscopy and cross-sectional high-resolution transmission electron microscopy. The possible mechanism is presumed to be that the nitrogen ion irradiation induces the structure modification (converting sp³-bonded carbons into sp²-bonded ones) in UNCD films.     

Electromagnetic interference shielding effectiveness of carbon-based materials prepared by screen printing

Screen printing, as a simple and efficient method, is used to fabricate a carbon-based film for electromagnetic interference (EMI) shielding applications. The results show that carbon nanotube (CNT) sheets are more effective in providing EMI shielding compared to graphite and carbon black sheets in abroad-band frequency range due to better electron transmission. A thin printed 150 μm 15 wt% CNT film exhibits similar shielding performance to a thicker 1.5 mm 15 wt% CNT epoxy composites, illustrating that screen printing could be a promising approach to fabricate thin EMI shielding films for commercial applications.     

Deposition of amorphous carbon films from C60 fullerene sublimated in electron beam excited plasma

C₆₀ fullerene clusters are used as a carbon source for amorphous carbon films deposition in an electron beam excited plasma. C₆₀ clusters are sublimated by heating a ceramic crucible containing the C₆₀ powders up to 850 °C, which is located in a highly vacuumed process chamber. The sublimated fullerene powders are injected to the electron beam excited argon plasma and dissociated to be active species that are propelled toward the substrates. Consequently, the carbon species condense as a thin film onto the negatively biased substrates that are immersed in the plasma. Deposition rates of approximately 1.0 μm/h and the average surface roughness of 0.2 nm over an area of 400 μm² are achieved. Decomposition of the C₆₀ fullerene after injecting into the plasma is confirmed by optical emission spectroscopy that shows existence of small carbon species such as C₂ in the plasma. X-ray diffraction pattern reveals that the microstructure of the film is amorphous, while fullerene films deposited without the plasma show crystalline structure. Raman spectroscopic analysis shows that the films deposited in the plasma are one of the types of diamond-like carbon films. Different negative bias voltages have been applied to the substrate holder to examine the effect of the bias voltage to the properties of the films. The nano-indentation technique is used for hardness measurement of the films and results in hardness up to about 28 GPa. In addition, the films are droplet-free and show superior lubricity.     

Electrodeposition of hard magnetic films and microstructures

Electrochemical deposition of materials with hard magnetic properties in the as-deposited state is essential for the efficient integration of micro-magnetic components into MEMS devices. Here we discuss the growth process and the microstructure-magnetic properties correlation for two Co-rich alloys, Co-Ni-P and Co-Pt. Under suitable synthesis conditions, these materials exhibit perpendicular anisotropy and hard magnetic properties in the as-deposited state; in addition, such properties are maintained up to several micrometer film thickness through close control of the film microstructure. In the case of Co-Ni-P films we achieved a saturation magnetization of 1.21 T (963 emu/cm³), perpendicular coercivity up to 188 kA/m (2.36 kOe) at a thickness of 10 μm, and energy products up to 4.2 kJ/m³. Co-rich Co-Pt films were grown on several substrates - Cr, Cu(0 0 1), Cu(1 1 1), and Ru(0 0 0 1) - in order to control magnetic anisotropy and achieve optimum hard magnetic properties. Cu(1 1 1) contributes to stabilize the hexagonal hcp phase at high current density yielding excellent hard magnetic properties, although only in films thicker than 100 nm; saturation magnetization in these films was about 1.04 T (828 emu/cm³). Perpendicular coercivities up to 485.6 kA/m (6.1 kOe) were obtained in 1 μm thick film deposited at 50 mA/cm². Ru(0 0 0 1) seed layers provide an appropriate interface structure to further facilitate the epitaxial growth of hcp films, yielding hard magnetic properties and perpendicular coercivity with a squareness ∼1 in films as thin as 10 nm. The hard magnetic properties were only marginally compromised at large film thickness. Deposition at higher current density (50 mA/cm²) favored markedly improved hard magnetic properties. The Co-Pt films on Ru exhibited perpendicular anisotropy with anisotropy constant up to 1.2 MJ/m³. The electrodeposition process was further extended to fill lithographically patterned hole arrays (850 nm diameter, center-to-center distance 2550 nm and about 700 nm thick resist), yielding arrays of micron-sized hard magnetic cylinders with perpendicular coercivity of 361 kA/m (4.54 kOe) and high squareness.     

Preparation and characterization of highly conductive transparent films with single-walled carbon nanotubes for flexible display applications

Dense, aligned single-walled carbon nanotubes (SWCNTs) were obtained by nitric acid treatment and the subsequent removal of metal impurities by HCl. The highly purified SWCNTs were dispersed with sodium dodecyl sulfate in order to obtain a stabilized suspension for spray coating on flexible polyethylene terephthalate (PET) substrate. The low sheet resistance of the resulting thin conductive film on the PET substrate was due to the interconnecting networks of highly purified SWCNT bundles. These bundles formed strong crisscross networks of nanotubes clustered together with well defined channels, thus improving the electrical and optical properties of the film. Its sheet resistance varied from 956 to 472 Ω/square with 85% optical transmittance at a wavelength of 550 nm. The films may be potential candidates for flexible display applications.     

Graphite nanoplatelet pastes vs. carbon black pastes as thermal interface materials

Comparison of graphite nanoplatelet (GNP) and carbon black (CB) pastes as thermal interface materials shows that the optimum filler content for attaining the maximum thermal contact conductance (copper proximate surfaces, roughness 15 μm) are 2.4, 15 and 2.4 vol.% for GNP, CB (Tokai) and CB (Cabot), respectively. Except for CB (Cabot), the optimum filler content is diminished when the roughness is decreased from 15 to 0.009 μm. Comparing the fillers at their respective optimum contents shows that (i) GNP is similarly effective as CB (Tokai) for rough (15 μm) surfaces, but is less effective than CB (Tokai) for smooth (0.009 μm) surfaces, and (ii) GNP is more effective than CB (Cabot) for rough surfaces, but is slightly less effective than CB (Cabot) for smooth surfaces. GNP gives higher thermal conductivity and greater bond line thickness than CB (Tokai or Cabot), whether the comparison is at the same filler content or at the respective optimum filler contents. In spite of the high thermal conductivity, the effectiveness of GNP is limited, due to the high bond line thickness. CB (Tokai) gives higher thermal conductivity than CB (Cabot), thus causing CB (Tokai) to be more effective than CB (Cabot).