Radical-injection Plasma-enhanced Chemical Vapor Research Articles

Nitrogen admixture effects on growth characteristics and properties of carbon nanowalls

The plasma functionalization of carbon nanowalls (CNWs) is of great interest due to their potential applications in electron field emission and energy storage devices. In this study, the effects of nitrogen on the growth and properties of CNWs are thoroughly investigated by varying a wide range of the N2 concentrations in the CH4/H2/N2 discharge plasma. Nitrogen-doped carbon nanowalls (NCNWs) were synthesized in a single-step growth using the hydrogen radical injection plasma-enhanced chemical vapor deposition technique. The formation of dense NCNWs was found to be enhanced by nitrogen and was three times higher in the sample with a 150 sccm N2 flow rate than in the sample without N2 addition (N-0). As the N2 concentration increased from 0 to 200 sccm, the morphology of CNWs changed from relatively straight to curly-like nanowall structures. A high-resolution optical emission spectroscopic observation shows that as N2 flow increased, CN radicals became the dominant species, suppressing the formation of C2 and CH. Photoelectron spectroscopy analysis revealed the nitrogen doping effect on graphene layers at high N2 concentrations. According to Raman and Transmission Electron Microscopy analyses, the NCNWs had more branched and thicker nanowalls with higher defect concentrations than the N-0 sample. The wettability of NCNWs was improved, particularly for the sample with a N2 flow rate of 150 sccm.

Low-temperature growth at 225 °C and characterization of carbon nanowalls synthesized by radical injection plasma-enhanced chemical vapor deposition

The synthesis of carbon nanowalls (CNWs) necessitated a substrate heating temperature above 600 °C. This study describes a low-temperature growth at 225 °C and characterization of CNWs synthesized by the radical injection plasma-enhanced chemical vapor deposition. To investigate the effect of temperature on the growth process, CNWs were synthesized at various temperatures ranging from 200 °C to 700 °C. The morphology of the CNWs observed with a scanning electron microscope shows that wall density increases as substrate temperature decreases. The Raman spectroscopy analysis indicates that CNWs grown at 225 °C have higher defect levels than those grown at higher temperatures, such as 700 °C. Transmission electron microscopy confirmed the presence of multiple graphene layers in the CNWs grown at 225 °C. The water contact angle results revealed that CNWs grown at 225 °C had higher hydrophobicity than those grown at higher temperatures, opening up the potential for CNW applications.

Synthesis of highly dense and multi-branched carbon nanowalls by two-step growth combining different plasma chemical vapor deposition methods

We report a novel structure of carbon nanowalls (CNWs) synthesized by a two-step growth method using a radical injection plasma-enhanced chemical vapor deposition (RI-PECVD) as combined with a capacitively coupled plasma chemical vapor deposition (CCP-CVD). Scanning electron microscopy (SEM) observation shows that the CNWs grown by this method exhibit a multi-branched morphology with an average wall distance of ∼20 nm and a density of ∼74 wall units/μm2, which is more than 5 times higher than that of CNWs synthesized by the single-step RI-PECVD method. These branched-CNWs are crystalline and comprised of multilayer graphene as confirmed by the Raman and high-resolution transmission electron microscopy (HRTEM) analyses. A static water contact angle of 150° was obtained for the multi-branched CNWs indicating a superhydrophobic property. A possible growth mechanism of the branched-CNWs was also proposed through the investigation of the time-dependent growth from the second step.

Scaffolds with isolated carbon nanowalls promote osteogenic differentiation through Runt-related transcription factor 2 and osteocalcin gene expression of osteoblast-like cells

Carbon nanowalls (CNWs) with average wall-to-wall distances ranging from 100 to 3300 nm were synthesized using a radical injection plasma-enhanced chemical vapor deposition system. Application of a negative high voltage to the growth substrate using an inductor energy storage (IES) circuit provided CNWs with wall-to-wall distances depending on the nano-second pulse voltage of the IES circuit. Sparse isolated CNWs with average wall-to-wall distances of 700 nm were used for culturing Saos-2 cells. These cells showed better adhesion than the control after 2 days’ incubation and enhanced gene expression of the osteogenic differentiation genes Runt-related transcription factor 2 (Runx2) and osteocalcin after 10 days’ incubation. Sparse isolated CNW scaffolds hold promise for regulating the differentiation of osteoblast-like cells.

Effect of electrical stimulation on proliferation and bone-formation by osteoblast-like cells cultured on carbon nanowalls scaffolds

Carbon nanowalls (CNWs) were synthesized by radical injection plasma-enhanced chemical vapor deposition and used as scaffolds for cell culture. The proliferation of osteoblast-like cells (Saos-2) was enhanced on the CNW scaffold upon electrical stimulation (ES) with 10 Hz square pulses at a current of 226 nA. However, after incubation with ES for 10 d, differentiation of the cells toward bone formation was suppressed.

Optical Properties of Evolutionary Grown Layers of Carbon Nanowalls Analyzed by Spectroscopic Ellipsometry

Carbon nanowalls (CNWs), vertically standing graphene sheets, grown by the radical injection plasma-enhanced chemical vapor deposition system were analyzed by spectroscopic ellipsometry. The refractive indexes (n), extinction coefficients (k), and optical band gaps (Eg) of evolutionary growth layers were evaluated using the Tauc–Lorentz model with the effective medium approximation. It was observed that an amorphous carbon interfacial layer with n of 1.9–2.0 was formed prior to the growth of CNWs with n of 1.2–1.5. Moreover, the imaginary parts of complex dielectric functions analyzed using the Tauc–Lorentz model indicate the possibility that the CNWs have semiconducting features.

Initial growth process of carbon nanowalls synthesized by radical injection plasma-enhanced chemical vapor deposition

We synthesized carbon nanowalls (CNWs) using radical injection plasma-enhanced chemical vapor deposition. The initial growth process of CNWs was investigated with and without O2 gas addition to a C2F6 capacitively coupled plasma with H radical injection. In the case of the CNW synthesis without the addition of O2 gas, scanning electron microscopy (SEM), transmission electron microscopy, x-ray photoelectron spectroscopy (XPS), and Raman spectroscopy revealed that a 10-nm-thick interface layer composed of nanoislands was formed on a Si substrate approximately 1 min prior to CNW formation. In contrast, with O2 gas addition, SEM and XPS revealed that an interface layer was not formed and that CNWs were grown directly from nanoislands. Moreover, Raman spectroscopy suggested that the interface layer was composed of amorphous carbon and that O2 gas addition during CNW growth is effective for achieving a high graphitization of CNWs. Therefore, O2 gas addition has the effect of reducing the amorphicity and disorder of CNWs and controlling CNW nucleation.

Highly reliable growth process of carbon nanowalls using radical injection plasma-enhanced chemical vapor deposition

Two-dimensional carbon nanostructures, carbon nanowalls (CNWs), were fabricated on a Si substrate using radical injection plasma-enhanced chemical vapor deposition, employing fluorocarbon (C2F6) and hydrogen (H2) mixtures. The influence of the surface conditions of the chamber wall on CNW growth was investigated in order to determine the optimum conditions for CNW growth with high stability and reproducibility. In order to monitor the surface conditions of the chamber wall, optical emission spectroscopy in the plasma was measured, and the correlation between CNW growth and the surface conditions in the chamber wall was investigated. The growth rate and morphology of grown CNWs were determined to be influenced by the surface conditions of the chamber wall. Furthermore, O2 plasma chamber cleaning followed by predeposition for passivation was found to be effective for maintaining steady conditions to attain CNWs with high reproducibility.