Structural modification and enhanced electron emission from multiwalled carbon nanotubes grown on Ag/Fe catalysts coated Si-substrates

Multiwalled carbon nanotubes and carbon nano-filaments were grown using Fe as the main catalyst and Ag as a co-catalyst by microwave plasma enhanced chemical vapour deposition. In this work we demonstrate the growth behaviour of carbon nanotubes (CNTs) grown on pure Fe-film and Ag–Fe films. We find that using Ag film beneath Fe film significantly abate the catalyst–substrate interactions by acting as a barrier layer as well as enhances the nucleation sites for the growth of CNTs due to the limited solubility with Fe and silicon. Scanning electron microscopy and transmission electron microscopy studies were carried out to image the microstructures of the samples. It was observed that the length of Fe catalyzed CNTs was ∼500 nm and Ag–Fe catalyzed CNTs varied from ∼600 nm to 1.7 μm. Micro Raman spectroscopy confirmed the improved crystalline nature of Ag–Fe CNTs. It was found that I_D/I_G ratio for Fe catalyzed CNTs was ∼1.08 and for Ag–Fe catalyzed CNTs was ∼0.7. The Ag–Fe catalyzed CNTs were found to be less defective as compared to Fe catalyzed CNTs. Field emission measurements using diode configuration, showed that electron emission from Ag–Fe catalyzed CNTs was much stronger as compared to Fe catalyzed CNTs. The threshold field for Ag–Fe catalyzed CNTs was (2.6 V μm⁻¹) smaller as compared to Fe catalyzed CNTs (3.8 V μm⁻¹) and thus shows better emission properties. This enhancement in electron emission mechanism as a result of introduction of Ag underlayer is attributed to the increased emitter sites and improved crystallinity.     

Structural modifications and enhanced Raman scattering from multiwalled carbon nanotubes grown on titanium coated silicon single crystals

Multiwalled carbon nanotubes (MWCNTs) were grown on 10 nm iron (Fe) film by microwave plasma enhanced chemical vapor deposition using titanium (Ti) film as an interlayer. The Ti interlayer of thickness 5 nm-20 nm was sandwiched between Fe and silicon (Si) using thermal evaporation. Enhanced Raman response was observed in MWCNTs with increasing Ti interlayer thickness. This was related with the plasmonic effects occurring at the interface of the CNTs and the metallic support in a three layer system (Ti-Fe-CNTs). The increase in the G mode optical strength is attributed to surface enhanced resonance Raman scattering. Moreover, the increase in the D-mode and 2D-mode intensity is explained on the basis of double resonance effects. The crystallinity in the samples was calculated using I_D/I_G ratio. It was found that that I_D/I_G ratio decreases in three layer system with increasing Ti interlayer thickness as compared to a two layer (Fe-CNTs) system as reported earlier.     

High rate growth highly crystallized microcrystalline silicon films using SiH4/H2 high-density microwave plasma

The plasma parameter for fast deposition of highly crystallized microcrystalline silicon (μc-Si) films with low defect density is presented using the high-density and low-temperature microwave plasma (MWP) of a SiH₄-H₂ mixture. A very high deposition rate of ∼ 65 Å/s has been achieved at SiH₄ concentration of 67% diluted in H₂ with high Raman crystallinity I_c / I_α > 3 and low defect density of 1-2 × 10¹⁶ cm^− 3 by adjusting the plasma condition. Contrary to the conventional rf plasma, the defect density of the μc-Si films strongly depend on substrate temperature T_s and it increased with increasing T_s despite T_s below 300 °C, suggesting that the real surface temperature at the growing surface was higher than the monitored value. The sufficient supply of deposition precursors such as SiH₃ at the growth surface under an appropriate ion bombardment was effective for the fast deposition of highly crystallized μc-Si films as well as the suppression of the incubation and transition layers at the initial growth stage.     

Study of plasma enhanced chemical vapor deposition of ZnO films by non-thermal plasma jet at atmospheric pressure

Plasma enhanced chemical vapor deposition using a non-thermal plasma jet was applied to deposition of ZnO films. Using vaporized bis(octane-2,4-dionato)zinc flow crossed by the plasma jet, the deposition rate was as high as several tens of nm/s. From the results of infrared spectra, the films deposited at the substrate temperature T_sub = 100 °C contained a significant amount of carbon residue, while the films prepared at T_sub = 250 °C showed less carbon fraction. The experimental results confirmed that the plasma jet decomposed bis(octane-2,4-dionato)zinc in the gaseous phase and on the substrate, and that there should be the critical T_sub to form high-quality ZnO films in the range from 100 to 250 °C.     

Effects of applied power on hydrogenated amorphous carbon (a-C:H) film deposition by low frequency (60 Hz) plasma-enhanced chemical vapor deposition (PECVD)

Hydrogenated amorphous carbon (a-C:H) films were deposited onto glass substrates using low frequency (60 Hz) plasma-enhanced chemical vapor deposition and the effects of the applied power on a-C:H films deposition were investigated. During deposition, the electron temperature and the density of CH₄-H₂ plasma were 2.4-3.1 eV and about 10⁸ cm⁻³, respectively. The main optical emission peak of the carbon species observed in the CH₄-H₂ plasma is shown to be excited carbon CH* at 431 nm. The sp³/sp² ratio, band gap, hydrogen content, and refractive index of a-C:H films gradually increased up to a power of 25 W and then saturated at higher power. This tendency is similar to the variation of plasma parameters with varying applied power, thereby indicating that a strong relationship exists between the properties of the films and the plasma discharge.     

Growth of well-aligned carbon nanotubes by RF-DC plasma chemical vapor deposition

Highly aligned carbon nanotubes (CNTs) were grown under high sheath electric field and gas pressure conditions by the radio frequency (RF) plasma-enhanced direct current (DC) plasma chemical vapor deposition (CVD) method due to a stabilized DC discharge. The uniform growth of highly aligned multi-walled CNTs was achieved over the entire surface area of a 50 × 50 mm² iron foil. The growth of multi-walled CNTs on a 75 × 75 mm² iron foil was also confirmed.     

Effect of a pulsed Nd:YAG laser irradiation on multi-walled carbon nanotubes film

Multi-walled carbon nanotubes (MWCNTs) film have been analyzed by Raman spectroscopy to clarify the effect of a pulsed Nd:YAG laser heating. The MWCNTs film surface was flashed with the fundamental harmonic (λ = 1064 nm) or the second harmonic (λ = 532 nm) of a single pulse of Nd:YAG laser in the air. The dynamics of pulsed nanosecond laser heating process was simulated by the solution of the one-dimensional heat conduction equation. At the laser fluence of 500 mJ/cm² with Nd:YAG laser (λ = 1064 nm), the surface reached the maximum temperature 1395 °C at 12 ns. Moreover, the Raman spectroscopy of MWCNTs films before and after irradiation were measured. The intensity of the two characteristic Raman shifts I_D (defect-mode) and I_G (graphite-mode) was measured by the Raman spectroscopy. The maximum surface temperature was calculated and compared with the I_G/I_D ratio of MWCNTs film. The graphitization occurred on the sample after irradiation.     

Pt-modified carbon nanotube networked layers for enhanced gas microsensors

Carbon nanotubes (CNTs) networked films have been grown by chemical vapor deposition (CVD) technology onto miniaturized low-cost alumina substrates, coated by nanosized Co-catalyst for growing CNTs, to perform chemical detection of toxic gasses (NO₂ and NH₃), greenhouse gasses (CO₂ and CH₄) and domestic safety gasses (CO and C₂H₅OH) at an operating sensor temperature of 120 °C. The morphology and structure of the CNTs networks have been characterized by scanning electron microscopy (SEM). A dense network of bundles of multiple tubes consisting of multi-walled carbon nanostructures appears with a maximum length of 1-5 μm and single-tube diameter varying in the range of 5-40 nm. Surface modifications of the CNTs networks with sputtered Platinum (Pt) nanoclusters, at tuned loading of 8, 15 and 30 nm, provide higher sensitivity for significantly enhanced gas detection compared to un-decorated CNTs. This could be caused by a spillover of the targeted gas molecules onto Pt-catalyst surface with a chemical gating into CNTs layers. The measured electrical conductance of the functionalized CNTs upon exposures of a given oxidizing and reducing gas is modulated by a charge transfer model with p-type semiconducting characteristics. The effect of activated carbons as chemical filters to reduce the influence of the domestic interfering alcohols on CO gas detection has been studied. Functionalized CNT gas sensors exhibited better performances compared to unmodified CNTs, making them highly promising candidates for functional applications of gas control and alarms.     

Defect introduction in Ge during inductively coupled plasma etching and Schottky barrier diode fabrication processes

We have etched Sb-doped n-type (111) oriented Ge by inductively coupled plasma (ICP), using argon, and subsequently studied the defects that this process introduced as well as the effect of this etching on Schottky barrier diode quality. Deep level transient spectroscopy (DLTS) revealed that ICP etching introduced only one prominent defect, EP_0.31, in Ge with a level at 0.31 eV below the conduction band. The properties of this defect are different to those of defects introduced by other particle-related processing steps, e.g. sputter deposition and electron beam deposition, that each introduces a different set of defects. DLTS depth profiling revealed the EP_0.31 concentration was a maximum (3.6 × 10¹³ cm^− 3) close to the Ge surface and then it decreased more or less exponentially into the Ge. Annealing at 250 °C reduced the EP_0.31 concentration to below the DLTS detection limit. Finally, current-voltage (I-V) measurements as a function of temperature revealed that the quality of Schottky contacts fabricated on the ICP-etched surfaces was excellent at − 100 K the reverse leakage current at − 1 V was below 10 ¹³ A (the detection limit of our I-V instrumentation).     

Diluting and annealing effects on electromigration and morphology of chemical vapor-deposited copper films

The crystallization and orientation of chemical vapor-deposited copper films were investigated by means of X-ray diffraction. The ratios of Cu (1 1 1) peak intensity to Cu (2 0 0) [I(1 1 1)/I(2 0 0)] of the film deposited at different temperatures were plotted as a function of temperature. Then it can be found that the ratio of I(1 1 1)/I(2 0 0) increased with the deposition temperature, and 400 °C is the best one for electromigration when the films are grown in diluting N₂, and/or annealing by N₂ or by H₂. In addition, the morphology of copper films was characterized by atomic force microscopy, and it was found that the smoothness of the films grown in diluting N₂ and/or annealing by N₂ are improved, while the films annealing by H₂ have no significant changes.     

Improved electrochemical capacitive characteristics by controlling the carbon nanotube morphology and electrolyte solution concentration

Carbon nanotubes (CNTs) have been used as the electrochemical double layer in capacitor (EDLC) electrodes. CNTs were synthesized using thermal chemical vapor deposition (CVD) at a growth temperature of 750 °C by flowing C₂H₂. The surface morphology of the synthesized CNTs could be controlled with or without Al film deposition between the stainless (SUS) sheet and Fe catalyst film. Electrochemical measurements were performed in a three-electrode arrangement. H₂SO₄ with different concentrations was used as the electrolyte solution. The relation between the specific capacitance and the surface morphology of the CNTs and the electrolyte concentration were investigated. The results showed that the electrode formed using vertically aligned CNTs with higher electrolyte concentration exhibited higher specific capacitance.     

Effect of hydrogen plasma pretreatment on growth of carbon nanotubes by MPECVD

We have grown carbon nanotubes (CNTs) with a microwave (μW) plasma enhanced chemical vapor deposition (MPECVD) method, which has been regarded as one of the most promising candidates for the synthesis of CNTs due to the vertical alignment, the low temperature and the large area growth. We use methane (CH₄) and hydrogen (H₂) gas for the growth of CNTs. Ni catalytic layer (10 nm thick) were deposited on the Ti-coated Si substrate by RF magnetron sputtering method. In this work, we report the effects of pretreatment μW power on the growth of CNTs. We have pretreated the Ni catalytic layer in different μW power (600, 700, and 800 W) and grown same μW power (800 W). Scanning electron microscopy (SEM) images show Ni catalytic layer diameter and density are varied dependent with their pretreatment conditions. Raman spectroscopy of CNTs shows that I_D/I_G ratios and G-peak positions vary with pretreatment conditions.     

Surface characterization and nanomechanical properties of diamond-like carbon films synthesized by RF plasma enhanced chemical vapor deposition

Diamond-like carbon (DLC) films were synthesized by RF plasma enhanced chemical vapor deposition using acetylene as the carbon source and the effects of acetylene/nitrogen ratio in the reaction atmosphere, deposition pressure, and plasma post-treatment using different atmospheres on the surface roughness and mechanical properties of DLC films were investigated. Although the surface roughness, characterized by AFM, decreased as the acetylene/nitrogen ratio in the reaction atmosphere decreased, the hardness of DLC films measured by nanoindentation also decreased with the decrease of the acetylene/nitrogen ratio, which is consistent with the Raman results of the I_D/I_G ratio. Rougher films with higher residual stress were obtained when using a deposition pressure higher than 40.0 Pa (0.3 torr). For the effect of plasma post-treatment using different atmospheres, surface smoothing was found for the hydrogen plasma post-treatment, whereas nitrogen and argon plasma post-treatments resulted in surface roughening. Hydrogen plasma post-treatment was found to lower the surface roughness without significantly sacrificing the hardness.     

Synthesis of carbon coatings employing a plasma torch from an argon-acetylene gas mixture at reduced pressure

Amorphous hydrogenated carbon films (a-C:H) were formed on Si (1 1 1) wafers from an argon-acetylene gas mixture at a reduced pressure of 1000 Pa using a direct current (DC) plasma torch discharge. The Ar/C₂H₂ gas volume ratio varied from 1:1 to 8:1, the distance between plasma torch exit and the samples 0.04-0.095 m. The DC plasma torch technique allows the production of thick (∼90 μm) coatings at 0.3 μm/s growth rates. Raman spectra shape, D and G peak positions and the intensity ratio (I_D/I_G) show an increase of sp³ bond fraction with decreasing acetylene flow in argon plasma. Reflectance of the coatings deposited at Ar/C₂H₂=8:1 is high (∼97%) and slightly increases with increasing distance between samples and plasma torch exit.     

Improve photocurrent quantum efficiency of carbon nanotube by chemical treatment

High photocurrent quantum efficiency (QE) of carbon nanotubes (CNTs) is important to their photovoltaic applications. The ability of photocurrent generation of CNTs depends on their band structure and surface state. For given CNTs, it is possible to improve the QE of photocurrent by chemical modification. Here, we study the effects of simple chemical treatment on the QE of CNTs by measuring the photocurrent of macroscopic CNT bundles. The QE of the H₂O₂-treated CNT bundle reaches 5.28% at 0.1 V bias voltage at a laser (λ = 473 nm) illumination, which is 85% higher than that of the pristine sample. But the QE of the CNTs treated in concentrated HNO₃ is lower than that of the pristine sample. It shows that moderate chemical treatment can enhance the photocurrent QE and excessive chemical treatment will decrease the QE because of introducing lots of structural defects.     

Effect of substrate temperature and bias voltage on the crystallite orientation in RF magnetron sputtered AlN thin films

The crystal orientation and residual stress of AlN thin films were investigated using X-ray diffraction and substrate curvature method. The AlN films were deposited on Si(100) by RF magnetron sputtering in a mixed plasma of argon and nitrogen under various substrate negative bias V_s (up to − 100 V) and deposition temperature T_s up to 800 °C. The results show that lower temperature and moderate bias favor the formation of (002) plane parallel to the substrate surface. On the contrary, strong biasing beyond − 75 V and deposition temperature higher than 400 °C lead to the growth of (100) plane. At the same time nanoindentation hardness and compressive stress measured by substrate curvature method showed significant enhancement with substrate bias and temperature. The biased samples develop compressive stress while unbiased samples exhibit tensile or compressive stress depending on plasma power and temperature. The relationships between deposition conditions and crystallographic orientation of the films are discussed in terms of surface energy minimization and ion bombardment effects.     

Effect of oxygen plasma treatment on bonding states for columnar structured a-CNx thin films prepared by reactive sputtering

Amorphous carbon nitride (a-CN) thin films were deposited on silicon single crystal substrates by rf-reactive sputtering method using a graphite target and nitrogen gas. The substrate temperature was varied from room temperature (RT) to 853 K. After deposition, the effect of oxygen plasma treatment on bonding structures of the film surface has been studied by using an oxygen discharge at 16 Pa and rf power of 85 W. The chemical bonding states and film composition were analyzed by X-ray photoelectron spectroscopy (XPS), while film thickness was obtained from scanning electron microscopy (SEM) and ellipsometer. XPS study revealed that the films have NO₂ and NO₃ bonding structures when the films are deposited at temperatures higher than 673 K. After exposure to oxygen plasma, carbon in the film surface was etched selectively and this phenomenon was observed in all films. In contrast, the surface concentration of nitrogen was ket at constant values before and after oxygen plasma treatment. The NO₃ bonding state had dramatically increased after oxygen plasma treatment for films deposited at higher deposition temperatures. The film surfaces have been observed to change the function from hydrophobic to hydrophilic after oxygen plasma treatment.     

Influences of hydrocarbon radicals on the growth of Carbon nanotubes using heated-nozzle chemical vapour deposition

In this paper, the synthesis of carbon nanotubes (CNTs) on different substrates (i.e. Cu, Cr, Ta, Au, Ti, and Si) was performed using heated nozzle chemical vapour deposition (HN-CVD). The diffusion of high-order hydrocarbon radicals, i.e. C_aH_b (where a = 5, 6, and 7) generated through the heated nozzle (800-850 °C) via pyrolysis (they were verified by in-situ mass spectroscopy), which is placed a few centimeters above the substrate, plays an important role in CNT growth. Thus, the growth of CNTs deposited on the substrates, which were unavailable in thermal chemical vapour deposition (T-CVD) (540-600 °C), could be correlated to these precursors.     

Synthesis and luminescence properties for europium oxide nanotubes

A novel high temperature sensitive fluorescent nanocomposite has been successfully synthesized by an economic hydrothermal method using carbon nanotubes (CNTs), europium oxide, and sodium dodecyl benzene sulfonate (SDBS). To our great interest, the nanocomposites show high temperature sensitivity after calcinations at various temperatures, suggesting a synergetic effect of CNTs and europium oxide which leads to ultrahigh fluorescence intensity of europium oxide nanotubes. When the novel high temperature sensitive fluorescent nanocomposites were calcined beyond 620 °C for 4 h, the obtained nanocomposites have a strong emission peak at around 540 and 580 nm, due to the ⁵D₀ → ⁷F_j (j = 0, 1) forced electric dipole transition of Eu³⁺ ions. In turn, the emission spectra showed a slight blue shift. The intensity of this photoluminescence (PL) band is remarkably temperature-dependent and promotes strongly beyond 620 °C. This novel feature is attributed to the thermally activated carrier transfer process from nanocrystals and charged intrinsic defects states to Eu³⁺ energy levels. The novel high temperature sensitive fluorescent nanocomposite has potential applications in high temperature warning materials, sensors and field emission displays. It is also interesting to discover that CNTs have the effect of fluorescence quenching.     

Nucleation study of hydrogenated microcrystalline silicon (μc-Si:H) films deposited by VHF-ICP

Nucleation in the initial stage of hydrogenated microcrystalline silicon (μc-Si:H) film deposition by VHF inductivity-coupled plasma (ICP) has been investigated. When the SiH₄ concentration (R_SiH4 = [SiH₄] / ([SiH₄] + [H₂])) is 6%, the crystallization in the initial 1.1-2.4 nm film deposition is observed at the substrate temperature of 320 °C, while it is decreased to 150 °C by reducing the R_SiH4 to 3%. Furthermore, the nucleation is significantly promoted by H₂ plasma pretreatment as long as 90 s prior to μc-Si:H film deposition. The crystallinity was improved from 33 to 54% and the grain density was increased from 8.0 × 10¹⁰ to 1.7 × 10¹¹ cm^− 2 by the pretreatment. We confirmed no significant change in SiO₂ surface micro roughness after the H₂ plasma pretreatment. The chemical bond states at the SiO₂ surface before film deposition play an important role in nucleation.