Growth of carbon nanotube forests between a bi-metallic catalyst layer and a SiO2 substrate to form a self-assembled carbon–metal heterostructure

A special nanostructure was formed by the growth of carbon nanotubes (CNTs) between a substrate and a thin bi-metallic catalyst layer using a thermal chemical vapor deposition process. The catalyst layer is composed of adjacently disposed Cr and Ni phases formed prior to CNT growth. The Cr/Ni layer serves as a bi-metallic catalyst layer, which is pushed away from the substrate as a thin and continuous nanomembrane with the growth of CNTs. The self-assembled CNT–catalyst heterostructure possesses a smooth surface (RMS = 2.9 nm) with a metallic shine. Directly interlinked to the Cr/Ni layer, dense and vertically aligned multi-walled CNTs are found. Compared to conventional CNT films, the structure has significant advantages for CNT integration. From technology point of view, the structure allows further processing without impact on the CNTs as well as transfer of pristine vertically aligned CNTs to arbitrary substrates. Moreover, the as-grown CNT films provide an interface ideal for further electrical, thermal and mechanical contacting of CNT films. We present structural investigations of this special CNT–metal heterostructure. Furthermore, we discuss possible interface mechanisms during catalyst layer formation and CNT growth.     

Low temperature growth mechanisms of vertically aligned carbon nanofibers and nanotubes by radio frequency-plasma enhanced chemical vapor deposition

Using radio frequency-plasma enhanced chemical vapor deposition (RF-PECVD), carbon nanofibers (CNFs) and carbon nanotubes (CNTs) were synthesized at low temperature. Base growth vertical turbostratic CNFs were grown using a sputtered 8 nm Ni thin film catalyst on Si substrates at 140 °C. Tip growth vertical platelet nanofibers were grown using a Ni nanocatalyst in 8 nm Ni films on TiN/Si at 180 °C. Using a Ni catalyst on glass substrate at 180 °C a transformation of the structure from CNFs to CNTs was observed. By adding hydrogen, tip growth vertical multi-walled carbon nanotubes were produced at 180 °C using FeNi nanocatalyst in 8 nm FeNi films on glass substrates. Compared to the most widely used thermal CVD method, in which the synthesis temperature was 400–850 °C, RF-PECVD had a huge advantage in low temperature growth and control of other deposition parameters. Despite significant progress in CNT synthesis by PECVD, the low temperature growth mechanisms are not clearly understood. Here, low temperature growth mechanisms of CNFs and CNTs in RF-PECVD are discussed based on plasma physics and chemistry, catalyst, substrate characteristics, temperature, and type of gas.     

Physical and electrochemical properties of synthesized carbon nanotubes [CNTs] on a metal substrate by thermal chemical vapor deposition

Multi-walled carbon nanotubes were synthesized on a Ni/Au/Ti substrate using a thermal chemical vapor deposition process. A Ni layer was used as a catalyst, and an Au layer was applied as a barrier in order to prevent diffusion between Ni and Ti within the substrate during the growth of carbon nanotubes. The results showed that vertically aligned multi-walled carbon nanotubes could be uniformly grown on the Ti substrate (i.e., metal substrate), thus indicating that the Au buffer layer effectively prevented interdiffusion of the catalyst and metal substrate. Synthesized carbon nanotubes on the Ti substrate have the diameter of about 80 to 120 nm and the length of about 5 to 10 μm. The Ti substrate, with carbon nanotubes, was prepared as an electrode for a lithium rechargeable battery, and its electrochemical properties were investigated. In a Li/CNT cell with carbon nanotubes on a 60-nm Au buffer layer, the first discharge capacity and discharge capacity after the 50th cycle were 210 and 80 μAh/cm², respectively.     

Novel growth of carbon nanotubes on nickel nanowires

A novel growth phenomenon is presented in this paper where carbon nanotubes (CNT) were grown successfully on nickel (Ni) nanowire using chemical vapour deposition technique. The decomposed carbon from ethylene diffused through the surface of nanowires and precipitated into hollow cylindrical carbon structures. Nanotubes of various lengths are found to have grown along the length of the outer side of the nanowires and were firmly rooted to their walls. The presence of a thin layer of oxide (~ 3 nm) on the top surface of nanowires is believed to have promoted the growth of CNT. Raman, X-ray photoelectron (XPS) and electron energy loss spectroscopy (EELS) were conducted in order to understand the formation of nanotubes and verify their presence, their level of crystallinity and chemical bonding structure with nanowires. This hybrid nanostructure is also found to have ferromagnetic behaviour, which can be applied in devices such as magnetic sensors and spintronic devices that combine the unique properties of CNT and Ni nanowires.     

Catalyst‐Assisted Growth of Single‐Crystalline Hafnium Carbide Nanotubes by Chemical Vapor Deposition

Single‐crystalline hafnium carbide (HfC) nanotubes were synthesized by a one‐step catalyst‐assisted chemical vapor deposition (CVD) method. The typical nanotubes had uniform diameters of ~60 nm and wall thicknesses of ~15 nm and preferentially grew along [201]. From HRTEM/EELS analysis, the growth mechanism based on carbon nanotubes (CNT) tip growth and CNT‐templated reaction was proposed for explaining the formation of HfC nanotubes. According to the mechanism, CNTs were first formed by diffusion of C atoms on the surface of solid Ni catalyst particles. Then, gaseous Hf species reacted with C atoms from CNTs to form HfC nanotubes. During the entire growth process, Hf atoms did not participate in the catalytic reaction. Thus, this process was distinguished from the conventional vapor–liquid–solid process.     

High P–T Nano-Mechanics of Polycrystalline Nickel

We have conducted high P–T synchrotron X-ray and time-of-flight neutron diffraction experiments as well as indentation measurements to study equation of state, constitutive properties, and hardness of nanocrystalline and bulk nickel. Our lattice volume–pressure data present a clear evidence of elastic softening in nanocrystalline Ni as compared with the bulk nickel. We show that the enhanced overall compressibility of nanocrystalline Ni is a consequence of the higher compressibility of the surface shell of Ni nanocrystals, which supports the results of molecular dynamics simulation and a generalized model of a nanocrystal with expanded surface layer. The analytical methods we developed based on the peak-profile of diffraction data allow us to identify “micro/local” yield due to high stress concentration at the grain-to-grain contacts and “macro/bulk” yield due to deviatoric stress over the entire sample. The graphic approach of our strain/stress analyses can also reveal the corresponding yield strength, grain crushing/growth, work hardening/softening, and thermal relaxation under high P–T conditions, as well as the intrinsic residual/surface strains in the polycrystalline bulks. From micro-indentation measurements, we found that a low-temperature annealing (T < 0.4 T_m) hardens nanocrystalline Ni, leading to an inverse Hall–Petch relationship. We explain this abnormal Hall–Petch effect in terms of impurity segregation to the grain boundaries of the nanocrystalline Ni.     

Easy one-pot method to control the morphology of polyethylene/carbon nanotube nanocomposites using metallocene catalysts

An easy one pot method is demonstrated for the controlled periodical surface coating of polyethylene over multiwalled carbon nanotubes (MWCNT) by insitu polymerization of ethylene using highly active metallocene catalysts (Cp₂ZrCl₂ and Cp₂TiCl₂) in combination with methylalumoxane. The crystallinity of the nanocomposite was increased and its morphology could be tuned from “sausage” like to “shish-kebab” in the presence of CNT depending on the experimental condition and choice of metal atom.     

Synthesis of carbon nanotubes on metal alloy substrates with voltage bias in methane inverse diffusion flames

Vertically well-aligned multi-walled carbon nanotubes (MWNTs) with uniform diameters (∼15 nm) were grown on catalytic probes at high yield rates in an inverse diffusion flame (IDF) of a co-flow jet configuration using methane as fuel. Varied parameters investigated included: alloy composition (e.g. Fe, Ni/Cu, Ni/Cr/Fe), sampling positions within the flame structure, and voltage bias applied to the probe substrate. Spontaneous Raman spectroscopy was utilized to determine the local gas-phase temperature, as well as the concentrations of carbon-based precursor species (e.g. CO, C₂H₂) within the flame structure at specific locations of carbon nanotube (CNT) growth during synthesis. The variation of the aforementioned parameters strongly affects CNT formation, diameter, growth rate, and morphology.     

Enhanced electromagnetic interference shielding performance of geopolymer nanocomposites by incorporating carbon nanotubes with controllable silica shell

The development of construction materials with exceptional electromagnetic interference (EMI) shielding performance is urgently needed to restrict the admittance of electromagnetic (EM) radiation. In this work, silica (SiO₂)-coated carbon nanotubes (S-CNT) with different shell thicknesses (～7, ～10, and ～15 nm) were prepared by a sol-gel method. The effect of SiO₂ shell thickness on the EMI shielding performance of the resulting geopolymer nanocomposites was studied. The coated SiO₂ shell effectively facilitated the dispersion of CNT in the geopolymer matrix due to the chemical reaction between SiO₂ and the geopolymer. The dispersability of modified CNT could be further improved by increasing the thickness of the SiO₂ shell. However, electron delocalization was hindered by the insulating SiO₂ shell. The conductive nature of CNT was restored during geopolymerization when the SiO₂ shell was thin. A high EMI shielding effectiveness (SE) of 24.2 dB was achieved for the geopolymer nanocomposite containing 5 vol% S-CNT with a thin SiO₂ shell. The value achieved was more competitive than reported composites for construction when the sample thickness and filler content were considered.     

Synthesis of patterned carbon nanotube arrays for field emission using a two layer Sn/Ni catalyst in an ethanol flame

Patterned carbon nanotube (CNT) arrays on Si substrate have been fabricated by using a two layer Sn/Ni catalyst in a diffusion ethanol flame. Vertically well-aligned CNT arrays were achieved on a Si substrate without any catalyst pretreatment. The Sn underlayer activated the substrates for CNT growth with Ni as catalyst, and provided a good contact between CNTs and the substrate, which is useful for field emission. Since the adhesion of Sn/Ni nanoparticles to the substrate is very strong, the growth of the CNTs follows a base-growth mode. The thickness of the Sn underlayer largely determines the diameter and diameter distribution of the as-grown CNTs. The morphologies and field electron emission properties of CNT arrays grown on Si substrates with different thicknesses of Sn and growth times have been investigated. The variation of emission current density was less than 5% during a 4 h test under a field of 1.77 V/µm.     

Excellent Field Emission Properties of Short Conical Carbon Nanotubes Prepared by Microwave Plasma Enhanced CVD Process

Randomly oriented short and low density conical carbon nanotubes (CNTs) were prepared on Si substrates by tubular microwave plasma enhanced chemical vapor deposition process at relatively low temperature (350–550 °C) by judiciously controlling the microwave power and growth time in C₂H₂ + NH₃ gas composition and Fe catalyst. Both length as well as density of the CNTs increased with increasing microwave power. CNTs consisted of regular conical compartments stacked in such a way that their outer diameter remained constant. Majority of the nanotubes had a sharp conical tip (5–20 nm) while its other side was either open or had a cone/pear-shaped catalyst particle. The CNTs were highly crystalline and had many open edges on the outer surface, particularly near the joints of the two compartments. These films showed excellent field emission characteristics. The best emission was observed for a medium density film with the lowest turn-on and threshold fields of 1.0 and 2.10 V/μm, respectively. It is suggested that not only CNT tip but open edges on the body also act as active emission sites in the randomly oriented geometry of such periodic structures.     

Interfacial microstructure of the Si3N4/Si3N4 joint brazed with Cu–Pd–Ti filler alloy

Si₃N₄ ceramic was jointed with itself by active brazing with a Cu–Pd–Ti filler alloy. Interfacial microstructure of the Si₃N₄/Si₃N₄ joint was analyzed by EPMA, TEM and X-ray diffract meter. The results indicate that a TiN reaction layer with a thickness about 5 μm is formed at the interface between Si₃N₄ ceramic and filler alloy. The TiN reaction layer is composed of two zones: one next to the Si₃N₄ ceramic with grains of 100 nm and the other zone that connects with the filler alloy and has grains of 1 μm. The microstructure of the joint can be described as: Si₃N₄ ceramic/TiN layer with fine grains/TiN layer with coarsen grains/Cu[Pd] solid solution. Some new phases, such as Pd₂Si, PdTiSi, Ti₅Si₃ and TiN, were formed in the Cu[Pd] solid solution interlayer. With increasing brazing temperature from 1100 °C to 1200 °C, the thickness of the TiN reaction layer is not changed. Meanwhile, the amount and size of the TiN and Pd₂Si phases in the Cu[Pd] solid solution increase, while, the amount of the PdTiSi phase decreases.     

Microstructure and corrosion properties of Ni-TiN nanocoatings prepared by jet pulse electrodeposition

Ni–TiN nanocoatings were successfully prefabricated by jet pulse electrodeposition. The effect of jet rate on cross-sectional composition, microstructure, microhardness, and corrosion properties of nanocoatings was examined by X-ray photoelectron spectroscopy, high-resolution transmission electron microscope, atomic force microscopy, microhardness tester and electrochemical workstation. Results illustrated that Ni–TiN nanocoatings deposited at jet rate of 3 m/s exhibited high concentration of Ni and Ti with average concentrations of Ni and Ti of 54.5 at% and 19.8 at%, respectively. Average diameters of Ni grains and TiN nanoparticles in Ni–TiN nanocoatings prepared at 3 m/s were 47.8 nm and 30.5 nm, respectively. Nanocoatings deposited at 1 m/s, 3 m/s and 5 m/s showed surface root-mean-square roughness value of 95.431, 30.091 and 58.454 nm, respectively, and presented maximum microhardness of 789.5, 876.2, and 849.9 HV, respectively. Ni–TiN nanocoating obtained at 3 m/s demonstrated minimum I_corr and E_corr values of 1.02 × 10⁻³ mA/cm² and − 0.551 V, respectively, signifying to offer the best corrosion resistance.     

Interaction and Cooperative Nucleation of InAsSbP Quantum Dots and Pits on InAs(100) Substrate

An example of InAsSbP quaternary quantum dots (QDs), pits and dots–pits cooperative structures’ growth on InAs(100) substrates by liquid phase epitaxy (LPE) is reported. The interaction and surface morphology of the dots–pits combinations are investigated by the high-resolution scanning electron microscope. Bimodal growth mechanism for the both QDs and pits nucleation is observed. Cooperative structures consist of the QDs banded by pits, as well as the “large” pits banded by the quantum wires are detected. The composition of the islands and the pits edges is found to be quaternary, enriched by antimony and phosphorus, respectively. This repartition is caused by dissociation of the wetting layer, followed by migration (surface diffusion) of the Sb and P atoms in opposite directions. The “small” QDs average density ranges from 0.8 to 2 × 10⁹ cm⁻², with heights and widths dimensions from 2 to 20 nm and 5 to 45 nm, respectively. The average density of the “small” pits is equal to (6–10) × 10⁹ cm⁻² with dimensions of 5–40 nm in width and depth. Lifshits–Slezov-like distribution for the amount and surface density of both “small” QDs and pits versus their average diameter is experimentally detected. A displacement of the absorption edge toward the long wavelength region and enlargement toward the short wavelength region is detected by the Fourier transform infrared spectrometry.     

Electrochemical corrosion and materials properties of reactively sputtered TiN/TiAlN multilayer coatings

TiN/TiAlN multilayers of 2 μm thickness were successfully prepared by reactive DC magnetron sputtering method. XRD pattern showed the (1 1 1) preferential orientation for both TiN and TiAlN layers. XPS characterization showed the presence of different phases like TiN, TiO₂, TiON, AlN and Al₂O₃. Cross sectional TEM indicated the columnar growth of the coatings. The average RMS roughness value of 4.8 nm was observed from AFM analysis. TiN/TiAlN coating showed lower friction coefficient and lower wear rate than single layer coatings. The results of electrochemical experiments indicated that a TiN/TiAlN multilayer coating has superior corrosion resistance in 3.5% NaCl solution.     

Composite Electrodes for Electrochemical Supercapacitors

Manganese dioxide nanofibers with length ranged from 0.1 to 1 μm and a diameter of about 4–6 nm were prepared by a chemical precipitation method. Composite electrodes for electrochemical supercapacitors were fabricated by impregnation of the manganese dioxide nanofibers and multiwalled carbon nanotubes (MWCNT) into porous Ni plaque current collectors. Obtained composite electrodes, containing 85% of manganese dioxide and 15 mass% of MWCNT, as a conductive additive, with total mass loading of 7–15 mg cm⁻², showed a capacitive behavior in 0.5-M Na₂SO₄ solutions. The decrease in stirring time during precipitation of the nanofibers resulted in reduced agglomeration and higher specific capacitance (SC). The highest SC of 185 F g⁻¹ was obtained at a scan rate of 2 mV s⁻¹ for mass loading of 7 mg cm⁻². The SC decreased with increasing scan rate and increasing electrode mass.     

A layer-by-layer deposition mechanism for producing a pyrolytic carbon coating on carbon nanotubes

Pyrolytic carbon (PyC) was deposited on carbon nanotubes (CNTs) in order to modify them by introducing defects to their surface. The deposition of PyC was carried out at temperature between 800 and 1000 °C using propane as carbon source with or without a hydrogen carrier gas at low pressure of 20 kPa. The structure of PyC coatings was examined using transmission electron microscopy. The PyC coating could be distinguished from the original CNT walls due to the difference of the structure, with the coating showing a less orderly layer structure. When H₂ was introduced during deposition, PyC coating started to form at 900 °C, and the deposition rate increased rapidly with increasing temperature. Without H₂, PyC coating with a thickness of a few layers could be formed at temperatures between 800 and 900 °C in 10 min. The outmost layer of the PyC coating showed a structure of rough and curved carbon fragment. A layer-by-layer mechanism is proposed for the deposition consisting of alternating fragment formation (nucleation) and lateral growth to layer.     

Effect of TiN diffusion barrier layer on residual stress and carrier transport in flexible CZTSSe solar cells

The major drawback of flexible Cu₂ZnSn(S,Se)₄ (CZTSSe) solar cells is the inevitable residual stress in CZTSSe that considerably limits the efficiency and flexibility of these cells. Hence, in this work, TiN layers with varying thicknesses were sputtered between flexible Ti substrates and back contact Mo layers as diffusion barriers. The TiN barrier layer relieved residual stress, facilitated grain growth, and decreased the porosity of CZTSSe, thereby effectively suppressing the formation of carrier recombination paths and improving the mechanical strength of CZTSSe. Meanwhile, the band alignment of the CZTSSe/CdS heterojunction could be significantly tailored, leading to an improved ‘‘cliff-like’’ conduction band offset from ?0.49 eV to ?0.33 eV. Under the optimized TiN layer thickness of 50 nm, the power conversion efficiency of the fabricated flexible CZTSSe solar cell increased considerably from 3.43% to 4.85% along with high bending stability. Therefore, introducing the TiN diffusion barrier into traditional flexible CZTSSe solar cells improves the efficiency and flexibility of these devices. Moreover, this method could be a promising pathway for the large-scale production of smart, flexible, and portable electronic devices.     

Effect of heating process on the formation of nanoparticles of elastin model polypeptide, (GVGVP)251, by gamma-ray crosslinking

Nanoparticles were prepared by the thermosensitive aggregation of the elastin model polypeptide, (GVGVP)₂₅₁, and gamma-ray crosslinking. Three different heating processes, “slow heating,” “fast heating,” and “heat shock,” were used for the aggregation of the peptide, followed by gamma-ray crosslinking. Only the “heat shock” process successfully yielded stable nanoparticles with diameters of less than ca. 150 nm and a narrow size distribution. Circular dichroism (CD) spectrometry showed that this polypeptide formed a type-II β-turn structure when the temperature was increased to above the cloudy point in the case of the “heat shock” process; suggesting that this structure might contribute to stable nanoparticle formation by gamma-rays. CD spectrometry also suggested that this structure would be affected during the formation of stable crosslinked particles.     

Suppression of resist contamination during photolithography on carbon nanomaterials by a sacrificial layer

To suppress photoresist residues on carbon nanotubes (CNTs) resulting from photolithography, CNTs are covered by a sacrificial layer during photolithography. Using aluminum oxide (Al₂O₃) deposited by low temperature atomic layer deposition as the sacrificial layer, the fabricated suspended CNT field-effect transistors exhibit low on-state resistances as low as 91 kΩ and low gate hysteresis of 0.5 V in ambient air. The effectiveness of this technique in suppressing residues on CNTs was affirmed by atomic force microscopy, scanning electron microcopy, and micro Raman spectroscopy. The etchants of Al₂O₃, hydrofluoric acid and phosphoric acid, were found not to cause defects in CNTs while removing the sacrificial Al₂O₃ layer. With the protection of the Al₂O₃ layer, oxygen plasma ashing can be performed without causing further defects in CNTs, and the minimum thickness was determined to be between 9 nm and 17 nm. This simple and effective approach can be easily implemented in different resist-based lithography processes to fabricate carbon nano-devices that are free of resist residues.