Multi-walled carbon nanotube-based transparent conductive layers deposited on polycarbonate substrate

We characterize 10-nm outer diameter multi-walled carbon nanotubes (powder and dispersion), which will be used for the preparation of conductive layers on polycarbonate (PC) substrates. The optical, electrical, and mechanical characterization of the spin-coated deposited layers is shown and compared with results obtained for layers deposited in borosilicate glass substrates. In both glass and plastic, the layers have shown transmittance higher than 78% in the visible range and have passed the tape and pencil standard tests for adherence and hardness, respectively. However, the sheet resistance presented by layers deposited on PC is still much superior to that of layers deposited on glass and sintered at higher temperatures. Nevertheless, the results obtained still allow the use of such layers in antistatic applications.     

Effect of cross-linkable polymer on the morphology and properties of transparent multi-walled carbon nanotube conductive films

In this study, we fabricated optically transparent and electrically conductive multi-walled carbon nanotube (MWCNT) thin films using a spray-coating technique. The transparency and the electrical resistance of thin film are dependent on the nanotube content deposited on the polyethylene terephthalate (PET) substrate. Poly(acrylic acid) (PAA) and poly(N-vinyl pyrrolidone) (PVP) were used as adhesion promoters to improve MWCNT coating more significantly. The cross-linked polymer resulted in a superior bond between the MWCNTs and the substrates. The surface electrical resistance was significantly lower than the original sheet after nitric acid (HNO₃) treatment because of the removed surfactant and the increased interconnecting networks of MWCNT bundles, thus improving the electrical and optical properties of the films. Stronger interaction between the MWCNTs and the substrates resulted in lower decomposition of the polymer chain and less amounts of MWCNTs separated into the HNO₃ solution. The lower sheet electrical resistance of PVP/PAA-g-MWCNT conductive films on the PET substrate was because of a more complete conductive path with the cross-linked polymer than that without. Such an improved sheet of electrical resistance varied from 8.83 × 10⁴ Ω/□ to 2.65 × 10³ Ω/□ with 5.0 wt.% PVP/PAA-g-MWCNT sprayed on the PET after acid treatment.     

Crystalline patterning in Sm-doped sodium borate glass by CW Nd:YAG laser irradiation

Laser irradiation of glass materials has drawn much attention because this technique can offer a new processing method for spatially selected structural modification and/or crystallization in glass. Crystallized line and dot patterns at the micrometer scale were fabricated on the surface of Sm-doped sodium borate (Na₂O-B₂O₃) glass by irradiation of a continuous-wave Nd:YAG laser at λ = 1064 nm. The pattern sizes could be controlled by adjusting such parameters as scan rate, exposure time, and laser power. Analyses by Raman spectroscopy and X-ray diffraction revealed that the crystalline phase is Na₃Sm₂(BO₃)₃.     

碳纳米管悬浮液的光限幅特性实验研究

 通过超声波降解法制备了多壁碳纳米管的水-表面活性剂悬浮液,测量了其对于1 064 nm,脉宽10 ns Nd:YAG调Q脉冲激光的光限幅曲线。实验发现：入射激光能量密度较低时,出射能量密度随入射能量密度的增加而线性增加;当入射能量密度为160 mJ/cm²时,出射能量不再线性增加并且逐渐趋近于光限幅器的嵌位输出值,约16 mJ,同时,对激光的透过率从71%下降到15%。通过Z扫描和探针光实验以及45°散射角下散射能量、散射率随入射激光能量变化曲线的测量,对碳纳米管悬浮液的光限幅机理进行了研究。结果表明：其限幅机理可能源于碳纳米管吸收激光能量后升华产生的膨胀的碳气泡对入射激光产生的非线性散射;另外,非线性折射对光限幅效果也有一定的作用。     

New aspects on pulsed laser deposition of aligned carbon nanotubes

We have grown carbon nanotubes (CNT) by pulsed laser deposition (PLD) at 1000 °C in Ar atmosphere. A Nd/YAG laser was used for irradiation of a graphite target containing Ni and Co rods. High-resolution scanning electron microscopy (HRSEM) and transmission electron microscopy (TEM) images showed that “closed” carbon nanotubes were grown between clusters of metallic particles, so that the individual nanotubes were arranged in parallel to each other forming a shape of “Rope-Bridge”. The nanotubes structure was analyzed by high-resolution transmission electron microscopy (HRTEM) and their type was found to be of MWNT, containing about five SWNT. Total diameter was 5-20 nm and their length was about 1 μm. High homogeneous distribution carbon nanotubes were grown and different structures were observed such as well-aligned carbon nanotubes, bamboo-like and Y-junction carbon nanotubes.     

Direct laser patterning of self-assembled monolayer using elliptical laser beams: A theoretical parametric study

A theoretical quantitative analysis of processing parameters for application of an elliptical laser beam to achieve maximum patterning area is the focus of this study. Direct laser patterning (DLP) of self-assembled monolayers (SAM) is achieved by localized heating of the sample above the SAM desorption temperature. Through use of elliptical laser beams in the present work, three goals are achieved by analyzing the heat diffusion model and related thermo-kinetics model: (1) optimal working conditions (combination of laser power, scanning velocity and aspect ratio) for DLP to produce maximum feature size, or highest processing velocity at a given power; (2) identification of conditions that reduces the potential thermal damage to the substrate; (3) shedding light on issues related to uniformity or homogeneity of heating a substrate using an elliptical laser beam. A heat diffusion model is employed to provide the resulting surface temperature caused by elliptical laser beams, and the coupled thermo-kinetics model is used to determine the final SAM coverage generated by DLP. Parametric analysis revealed that 70–150 mW can be used to pattern feature sizes in the range of 2–10 times of equivalent circular beam size. It is also found that each elliptical laser beam has a unique optimal aspect ratio to result in the widest feature size for a given laser power and scanning velocity. The edge transition width increases with an increase of the aspect ratio. Keeping the aspect ratio of elliptical laser beam small (i.e. β<20), a sharp edge definition could be obtained; if an aspect ratio larger than 30 is used, a surface with gradual edge definition could be obtained.     

Transparent carbon nanotube coatings

Thin networks of carbon nanotubes (CNTs) are sprayed onto glass or plastic substrates in order to obtain conductive transparent coatings. Transparency and conductivity at room temperature of different CNT material are evaluated. CNT coatings maintain their properties under mechanical stress, even after folding the substrate. At a transparency of 90% for visible light we observe a surface resistivity of 1 kΩ/sq which is already a promising value for various applications.     

Fabrication of transparent double-walled carbon nanotubes flexible matrix touch panel by laser ablation technique

This study reports on the fabrication of transparent double-walled carbon nanotubes (DWNTs) flexible matrix touch panel using the method of laser ablation. We employed an Nd:YAG laser (1064 nm) to pattern transparent DWNT thin film pre-coated on a PET substrate and successfully fabricated a flexible matrix touch panel. By increasing the laser energy, the ablation depth of transparent DWNT flexible thin film is increased but the sheet resistance (Ω/sq) is decreased. When the laser energy intensity reaches 117 mJ/cm², the DWNTs can be completely ablated from transparent DWNT flexible thin film. This method is rapid, simple, applicable to large-area processing and thus is potential for mass production.     

Electric resistivity of multi-walled carbon nanotubes at high temperatures

The electric resistivity of a clean multi-walled carbon nanotube (MWNT) mat sample was studied at temperatures T between 300 and 1900 K. We found that the resistivity ρ decreases monotonously with increasing temperature without showing any sign of turn up. Our results can be well fitted with a power law of T^−α within the framework of one dimensional Luttinger liquid theory with α = 0.13 or with a simple thermally activated inter shell hopping model.     

Highly conductive and transparent carbon nanotube-based electrodes for ultrathin and stretchable organic solar cells

In this work, we have presented a freestanding and flexible CNT-based film with sheet resistance of 60 ?/ and transmittance of 82% treated by nitric acid and chloroauric acid in sequence. Based on modified CNT film as a transparent electrode, we have demonstrated an ultrathin, flexible organic solar cell(OSC) fabricated on 2.5-μm PET substrate. The efficiency of OSC, combined with a composite film of poly(3-hexylthiophene)(P3HT) and phenyl-C61 butyric acid methyl ester(PCBM) as an active layer and with a thin layer of methanol soluble biuret inserted between the photoactive layer and the cathode, can be up to 2.74% which is approximate to that of the reference solar cell fabricated with ITO-coated glass(2.93%). Incorporating the as-fabricated ITO-free OSC with pre-stretched elastomer, 50% compressive deformation can apply to the solar cells. The results show that the as-prepared CNT-based hybrid film with outstanding electrical and optical properties could serve as a promising transparent electrode for low cost, flexible and stretchable OSCs, which will broaden the applications of OSC and generate more solar power than it now does.     

Direct patterning of microelectrode arrays using femtosecond laser micromachining

Micron-resolution microelectrodes and microelectrode arrays are commonly used in Lab-on-a-chip applications, typically for particle and fluidic sensing or pumping applications. The common method of fabricating such structures is to use conventional photolithography, which involves several steps, any of which can affect the quality and dimension of the final structure. Here we present an alternative method of creating microelectrodes using direct laser patterning. This is a significantly simpler and faster fabrication route requiring a single patterning step, and which also allows design changes to be implemented quickly, without having to re-manufacture a photolithographic mask. To confirm the suitability of this approach to fabricating microelectrodes, a complex multielectrode array design for neuron stimulation was directly laser-patterned.     

Direct fabrication of periodic patterns with hierarchical sub-wavelength structures on poly(3,4-ethylene dioxythiophene)-poly(styrene sulfonate) thin films using femtosecond laser interference patterning

A simple optical interference method for the fabrication of simply periodic and periodic with a substructure on poly(3,4-ethylene dioxythiophene)-poly(styrene sulfonate) using femtosecond laser interference patterns is demonstrated. The femtosecond laser pulse was split by a diffractive beam splitter and overlapped with two lenses. Homogeneous periodic arrays could be fabricated even using a single laser pulse. In addition, multipulse irradiation resulted in reproducible sub-wavelength ripples oriented perpendicularly to the laser polarization with spatial period from 170 to 220 nm (around one-fourth of the laser wavelength). In addition, the observed size of the spatial period was not affected by the number of incident laser pulses or accumulated energy density. Using high energy pulses it was possible to completely remove the PEDOT:PSS layer without inducing damage to the underneath substrate.     

The significance of carbon on the microstructure of TiAlNC coatings deposited by reactive magnetron sputtering

A series of TiAlCN coatings with different carbon contents have been deposited by a reactive sputtering of TiAl target under an environment with a mixture of Ar, N₂ and CH₄ gases. Microstructural changes, starting from pure TiAlN and then into TiAlCN with the increase of the carbon content, have been clearly demonstrated. This occurrence is due to the carbon atom substitution that results in a small alternation of the interplannar lattice parameter. The coating initially shows a strong preferred (1 1 1) texture in the pure TiAlN but becomes more randomly oriented at the higher carbon contents. Evidence was found for the presence of a free carbon phase, which provides the possibility to accomplish the self-lubricant coating.     

Periodic patterning of silicon by direct nanosecond laser interference ablation

The production of periodic structures in silicon wafers by four-beam is presented. Because laser interference ablation is a single-step and cost-effective process, there is a great technological interest in the fabrication of these structures for their use as antireflection surfaces. Three different laser fluences are used to modify the silicon surface (0.8 J cm⁻², 1.3 J cm⁻², 2.0 J cm⁻²) creating bumps in the rim of the irradiated area. Laser induced periodic surface structures (LIPSS), in particular micro and nano-ripples, are also observed. Measurements of the reflectivity show a decrease in the reflectance for the samples processed with a laser fluence of 2.0 J cm⁻², probably caused by the appearance of the nano-ripples in the structured area, while bumps start to deteriorate.     

Patterning of nanoparticulate transparent conductive ITO films using UV light irradiation and UV laser beam writing

Indium tin oxide (ITO) thin film is one of the most widely used as transparent conductive electrodes in all forms of flat panel display (FPD) and microelectronic devices. Suspension of already crystalline conductive ITO nanoparticles fully dispersed in alcohol was spun, after modifying with coupling agent, on glass substrates. The low cost, simple and versatile traditional photolithography process without complication of the photoresist layer was used for patterning ITO films. Using of UV light irradiation through mask and direct UV laser beam writing resulted in an accurate linear, sharp edge and very smooth patterns. Irradiated ITO film showed a high transparency (∼85%) in the visible region. The electrical sheet resistance decrease with increasing time of exposure to UV light and UV laser. Only 5 min UV light irradiation is enough to decrease the electrical sheet resistance down to 5 kΩ□.     

Effects of gas composition on the growth of multi-walled carbon nanotube

This paper studies the effects of different gas compositions on the growth of multi-walled carbon nanotube (MWCNT) films by using an electron cyclotron resonance chemical vapor deposition (ECR-CVD) method. The Raman spectrum was employed to explore the composition of the MWCNT films grown under different mixtures of C₃H₈ and H₂. The results showed that the optimum relative intensity ratio of the D band to G band (i.e., I_D/I_G) is 2 for the cases considered in this study. In addition, the morphology and microstructure of the MWCNTs were examined by field emission scanning electron microscopy (FE-SEM) and field emission gun transmission electron microscopy (FEG-TEM). Furthermore, atomic force microscopy (AFM) and scanning thermal microscopy (SThM) were used to study the surface topography and thermal properties of the MWCNTs.     

Electrical and electrochemical properties of carbon nanotube-based free standing LTO electrodes for current collector-free Li-ion batteries

The spinel lithium titanate oxide (Li₄Ti₅O₁₂, LTO) has been extensively studied as one of the most promising alternatives to carbon materials in energy conversion and storage devices, due to its high structural and thermal stability, rate capability, and excellent cycling stability. In this study, Li₄Ti₅O₁₂/multi-walled carbon nanotubes (LTO-MWCNTs) free-standing and flexible composite electrodes/buckypapers were prepared via tape casting technique and well compared with commercially available LTO. The structural, morphological, electrical and electrochemical properties of LTO-MWCNTs buckypaper as well as LTO were studied. The electrical conductivity of LTO-based buckypaper was found to be very high i. e, 4.4 × 10² Scm⁻¹ at room temperature. Further, the buckypaper prepared by synthesized LTO showed higher specific capacity (166 mAhg⁻¹) compared to commercially available LTO (137 mAhg⁻¹) at 0.2 C rate. The enhanced electrochemical performance of as-synthesized LTO-based buckypaper is mainly attributed to the higher electronic conductivity and homogeneous distribution of particles with its small size which facilitates large amount of active sites for lithium insertion and also short diffusion paths.     

One-pot, efficient functionalization of multi-walled carbon nanotubes with diamines by microwave method

Diamines are known to act as a medium to bind miscellaneous compounds to carbon nanotubes (CNT). However, they are commonly applied in a tedious manner. Here, multi-walled carbon nanotubes (MWCNTs) were functionalized by a series of diamine molecules (ethylenediamine, 1,6-hexamethylenediamine and 1,4-diaminobenzen) in a one-pot, rapid microwave-assisted method. Surface functionality groups and morphology of MWCNTs were analyzed by infrared spectroscopy, thermogravimetric analysis, Raman spectroscopy, scanning electron microscopy, and transmission electron microscopy. The results consistently confirmed the formation of diamines functionalities on MWCNTs, while the structure of MWCNT has remained relatively intact. This simple and efficient process may play an important role for realizing miscellaneous functionalization of CNTs.     

Synthesis of multi-walled carbon nanotubes for NH3 gas detection

It has been recently demonstrated that carbon nanotubes (CNTs) represent a new type of chemical sensor capable of detecting a small concentration of molecules such as CO, NO₂, NH₃.In this work, CNTs were synthesized by chemical vapor deposition (CVD) on the SiO₂/Si substrate by decomposition of acetylene (C₂H₂) on sputtered Ni catalyst nanoparticles. Their structural properties are studied by atomic force microscopy, high-resolution scanning electron microscopy (HRSEM) and Raman spectroscopy. The CNTs grown at 700 °C exhibit a low dispersion in size, are about 1 μm long and their average diameter varies in the range 25–60 nm as a function of the deposition time. We have shown that their diameter can be reduced either by annealing in oxygen environment or by growing at lower temperature (less than 600 °C).We developed a test device with interdigital Pt electrodes on an Al₂O₃ substrate in order to evaluate the CNTs-based gas sensor capabilities. We performed room temperature current–voltage measurements for various gas concentrations. The CNT films are found to exhibit a fast response and a high sensitivity to NH₃ gas.     

Synthesis, characterization and cytotoxicity of surface amino-functionalized water-dispersible multi-walled carbon nanotubes

Surface functionalization of multi-walled carbon nanotubes (MWCNTs), with amino groups via chemical modification of carboxyl groups introduced on the nanotube surface, using O-(7-azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyluronium hexafluorophosphate (N-HATU) and N,N-diisopropylethylamine (DIEA) is reported. The N-HATU coupling agent provides faster reaction rate and the reaction occurs at lower temperature compared to amidation and acylation-amidation chemistry. The amines, 1,6-hexanediamine (HDA), diethylenetriamine (DETA), triethylenetetramine (TETA) and 1,4-phenylenediamine (PDA) were used. The resulting materials were characterized with different techniques such as FTIR, XRD, elemental analysis, TGA, TEM, UV-vis spectroscopy and cyclic voltammetry. MWCNTs functionalized with PDA posses the best dispersibility and electron transfer properties in comparison to the others amines. Functionalized MWCNTs, at the concentrations between 1 and 50 μg ml⁻¹, were not cytotoxic for the fibroblast L929 cell line. However, the concentrations of MWCNTs higher of 10 μg ml⁻¹ reduced cell growth and this effect correlated positively with the degree of their uptake by L929 cells.