Formation of nanostructured carbon films in gas-discharge plasmas

Deposition of carbon materials from methane-hydrogen gas mixtures in a DC gas discharge is investigated. Parameters ensuring stable discharge conditions and synthesis of diamond and graphite-like films are determined. Optical emission spectroscopy is used to analyze the composition of the activated gas phase in the course of carbon film deposition. Synthesis of graphite-like carbon nanotubes and nanocrystallites is shown to correlate with the presence of C₂ dimers in the plasma. A noncatalytic mechanism of synthesis of nanostructured graphite in a carbon-containing gas phase is proposed.     

Plasma polymerization investigated by the comparison of hydrocarbons and perfluorocarbons

Plasma polymerization involves to a significant extent the abstraction of atoms attached to carbons, such as hydrogen and halogen atoms, during the process of forming polymers. This abstraction reaction plays a major role in the plasma polymerization of certain groups of organic compounds. However, because of the extremely high degree of crosslinking and branching, characteristic of most plasma polymers of interest or practical value, the analysis of surfaces and/or polymers by the conventional methods is greatly hampered. Utilizing the exceptionally large chemical shifts observable in ESCA C ls spectrum of fluorcarbons, the extent of fluorine-abstraction and the rearrangement of fluorine atoms which occur during the plasma polymerization of tetrafluoroethylene were investigated using an inductive rf discharge of the monomer. The distribution of polymer deposition and the corresponding changes in properties are examined as functions of the experimental parameters. The discharge power level, which can be characterized by J/kg monomer, was found to play a predominant role in determining the physicochemical reactions which occur during the plasma polymerization. Because of the characteristic abstraction reaction which occurs in the plasma polymerization, etching by the plasma of the gas product (i.e., H₂ or F₂) plays an extremely important role in the competitive ablation and polymerization (CAP) scheme of plasma polymerization.     

Structural and electrical properties of high-k HfO2 films modified by CHF3 and C4F8/O2 plasmas

As-deposited HfO₂ films were modified by CHF₃, C₄F₈, and mixed C₄F₈/O₂ plasmas in a dual-frequency capacitively coupled plasma chamber driven by radio frequency generators of 60 MHz as the high frequency (HF) source and 2 MHz as the low frequency source (60/2 MHz). The influences of various surface plasma treatments under CHF₃, C₄F₈, and C₄F₈/O₂ were investigated in order to understand the chemical and structural changes in thin-film systems, as well as their influence on the electrical properties. Fluorine atoms were incorporated into the HfO₂ films by either CHF₃ or C₄F₈ plasma treatment; meanwhile, the C/F films were formed on the surface of the HfO₂ films. The formation of C/F layers decreased the k value of the gate stacks because of its low dielectric constant. However, the addition of O₂ gas in the discharge gases suppressed the formation of C/F layers. After thermal annealing, tetragonal HfO₂ phase was investigated in both samples treated with CHF₃ and C₄F₈ plasmas. However, the samples treated with O-rich plasmas showed monoclinic phase, which indicated that the addition of O plasmas could influence the Hf/O ratio of the HfO₂ films. The mechanism of the t-HfO₂ formation was attributed to oxygen insufficiency generated by the incorporation of F atoms. The capacitors treated with C₄F₈/O₂ plasmas displayed the highest k value, which ascribed that the C/F layers were suppressed and the tetragonal phase of HfO₂ was formed. Good electrical properties, especially on the hysteresis voltage and frequency dispersion, were obtained because the bulk traps were passivated by the incorporation of F atoms. However, the H-related traps were generated during the CHF₃ plasma treatments, which caused the performance degradation. All the treated samples showed lower leakage current density than the as-deposited HfO₂ films at negative bias due to the reduced trap-assisted tunneling by the incorporation of F to block the electrons transferring from metal electrode to the trap level.     

Deposition of hydrogenated amorphous carbon nitride films by dielectric barrier discharge plasmas

Hydrogenated amorphous carbon nitride (a-C:N:H) films were synthesized from CH₄/N₂, C₂H₄/N₂ and C₂H₂/N₂ mixtures using dielectric barrier discharge (DBD) plasmas. Atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) were used to characterize the surface morphology, bonding structure, and composition of the a-C:N:H films. The influences of plasma parameters (discharge pressure in the range of 25-1000 Pa) and feed gases used on the composition and the structure of deposited films were systematically studied. The a-C:N:H films with the uniform surface structure were deposited by low-pressure DBD plasmas with various systems. Compared to the films deposited in C₂H₄/N₂ and C₂H₂/N₂ systems, the films deposited in the CH₄/N₂ system exhibit the relatively lower surface roughness and deposition rate. For all the films prepared in these three systems, increasing the discharge pressure leads to an increase in film surface roughness and deposition rate. Significant differences among the FTIR spectra of all deposited a-C:N:H films were also observed. Both FTIR and XPS spectra show that for all the films deposited in three different systems, increasing the N₂ fraction leads to a decrease in the H content of deposited a-C:N:H films and an increase in the N content. The properties of deposited films may change from those of polymerlike to diamond-like when the discharge pressure is increased. Correlations between the film properties and growth processes are discussed in this study.     

Permeability of C60 films deposited on polycarbonatesyloxane to N2, O2, CH4, and He gases

In this study, we report on the gas permeability of non-polymerized and polymerized fullerene films (thickness about 0.5 μm) grown on an organic polymer substrate, polycarbonatesyloxane (PCS), using a high vacuum deposition method. The photopolymerized C₆₀ films were prepared by a simultaneous thin film deposition and UV-vis irradiation method which was reported previously [V.A. Karachevtsev, P.V. Mateichenko, N.Y. Nedbailo, A.V. Peschanskii, A.M. Plokhotnichenko, O.M. Vovk, E.N. Zubarev, A.M. Rao, Carbon 42 (2004) 2091]. Raman spectroscopy revealed that ∼90% of the C₆₀ molecules are covalently linked to neighboring C₆₀ molecules in the photopolymerized film after 20 h of film deposition/irradiation. Permeability of the resulting membranes consisting of polymer PCS base and fullerene films to the N₂, O₂, CH₄, and He gases has been investigated. Our experiments revealed that the gas permeability properties are dependent on the age of the membrane. In particular, the aged membrane exhibited an enhanced permeability for O₂ and He gases in comparison to N₂ and CH₄, respectively.     

Spectroscopic study of an atmospheric pressure plasma generated for the deposition of titanium dioxide thin films

TiO₂ thin films are applied in various domains, e.g. air or water purification, self-cleaning surfaces etc. The deposition of titanium dioxide at industrial scale remains challenging. Atmospheric pressure plasma chemical vapor deposition methods are currently developed to provide an easy and viable method for deposition at industrial scale. Even though those methods lead to promising applicative coatings their formation mechanisms remain poorly investigated. In order to investigate the effect of the plasma parameters, i.e. plasma power and introduction of oxygen, on the plasma chemistry, optical emission spectroscopy (OES) is employed to monitor the various species present in the discharge. X-ray Photoelectron Spectroscopy (XPS) analyses of the deposited thin films are carried out and show that by either decreasing the plasma power or introducing oxygen the carbon impurities in the layer can be reduced. By comparing OES and XPS data, the ratio of carbon containing species (CH and C₂) to oxygen, i.e. I_CH/I_O or I_C2/I_O, in the discharge is shown to be related to the carbon/oxygen composition ratio in the layer.     

Research of microstructural characteristics on nanocrystalline diamond by microwave plasma CVD

In this study, the nanocrystalline diamond (NCD) films were carried out by microwave plasma chemical vapor deposition (CVD) with CH₄/Ar/H₂ gas concoction on Si substrate at moderate temperatures. The characteristics of NCD films were evaluated using scanning electron microscopy, Raman spectroscopy, transmission electron microscopy, optical emission spectroscopy and optical contact angle meter. The analytical results revealed that C₂ radial was the dominant species in the deposited process. From TEM observation, the NCD films were formed via the etching of hydrocarbons and a small amount of H₂ content additive into gas mixture has improved the aggregation of the nucleation film to form the NCD films. The more hydrophobic surfaces imply that NCD films are the potential biomaterial in the application of article heart valve or stent.     

Characteristics of an atmospheric‐pressure radio frequency‐driven Ar/H2 plasma discharge with copper wire in tube

This paper investigates a plasma discharge driven by a 13.56 MHz radio frequency (RF) power supply at atmospheric pressure, in which a copper wire is inserted in the discharge tube for the deposition of Cu films. The results show that the jet plasma formation originates from the discharge between the copper wire and induction coil because of its electrostatic field. The axial distribution of the plasma parameters in the RF plasma jet, namely the gas temperature, excitation temperature, and electron number density, is determined by diatomic molecule OH fitting, Boltzmann slope, and H_β Stark broadening, respectively. The discharge current significantly declines when a small amount of hydrogen is added to the argon as the plasma‐forming gas, and the gas temperature of discharge plasma increases considerably.     

Modification of polyethylene powder with an organic precursor in a spiral conveyor by hollow cathode glow discharge

Hexamethyldisiloxane (HMDSO) films were deposited on polyethylene (PE, (C₂H₄)_n) powder by hollow cathode glow discharge. The reactive species in different HMDSO/Ar plasmas were studied by optical emission spectroscopy (OES). Increasing the HMDSO fraction in the gas mixture additional compounds like CH_x, OH, SiC and SiO can be identified. After deposition the formed silicon and carbon containing groups (C–O, C=O, SiC and SiO) on the PE powder surface have been analyzed by X-ray photoemission spectroscopy (XPS). Changes in wettability depending on the HMDSO fraction were investigated by contact angle measurements (CAM). The free surface energy of the PE powder decreases with increasing HMDSO fraction in the process gas and encapsulation of the powder particles occurs. An aging effect of the plasma treated PE surface was observed depending on the process gas composition. The higher the HMDSO fraction the less is the aging effect of the plasma treated PE surface.     

Prediction of surface microtrenching by using neural network

Silicon oxynitride films were etched in a C₂F₆ inductively coupled plasma. A prediction model of microtrenching depth (MD) was constructed by using a neural network and a genetic algorithm. For a systematic modeling, etching data were collected by using a statistical experimental design. The process parameters and ranges were 400–1000 W, 30–90 W, 6–12 mTorr, and 30–60 sccm for source power, bias power, pressure, and C₂F₆ flow rate, respectively. The root mean-squared prediction error of the constructed model was about 0.019. The model was utilized to generate 3-D plots, which were used to examine etch mechanisms under various plasma conditions. Depending on the plasma conditions, parameter effects on MD were quite different. For most of the parameter variations, MD variations were strongly related to profile angle variations. The effect of bias power on MD seems to be dominated by polymer deposition due to the variations in C₂F₆ flow rates maintained in the chamber.     

Structural and phase composition of fullerene films deposited by high-power ion beams

Deposition of carbon films containing C₆₀ and C₇₀ fullerenes is an urgent problem, related to development of nanotechnologies and new nanomaterials. Such films have been obtained by ultrafast deposition of dense ablation plasma on a substrate; the plasma was generated as a result of irradiation of a graphite target by pulsed high-power ion beams. The structural and phase composition of the deposited films has been investigated.     

OES study of the gas phase during diamond films deposition in high power DC arc plasma jet CVD system

This paper used optical emission spectroscopy (OES) to study the gas phase in high power DC arc plasma jet chemical vapour deposition (CVD) during diamond films growth processes. The results show that all the deposition parameters (methane concentration, substrate temperature, gas flow rate and ratio of H₂/Ar) could strongly influence the gas phase. C₂ is found to be the most sensitive radical to deposition parameters among the radicals in gas phase. Spatially resolved OES implies that a relative high concentration of atomic H exists near the substrate surface, which is beneficial for diamond film growth. The relatively high concentrations of C₂ and CH are correlated with high deposition rate of diamond. In our high deposition rate system, C₂ is presumed to be the main growth radical, and CH is also believed to contribute the diamond deposition.     

电激励脉冲HF激光SF_6/C_2H_6工作气体的放电特性

研究了电激励脉冲HF激光工作介质SF6/C2H6混合气体的放电特性。通过对放电等离子体荧光图像和放电波形的测量,分析比较了不同条件下放电稳定性、剩余电压、能量沉积效率等特性参数的变化情况。实验结果表明:混合气体的放电过程存在主放电、剩余电压维持和电弧放电3个阶段,各阶段的放电特性有所差异;提高充电电压有利于放电能量的有效沉积,也会使不稳定的电弧放电提前;增加C2H6原子分数能起到抑制电弧放电的作用;混合气体总压的增加会导致剩余电压的提高以及辉光放电的能量沉积效率的降低;最佳的能量沉积出现在电弧放电阶段与辉光放电阶段即将融合的临界状态。     

Polymer Surface Functionalization Using Plasma,Ultraviolet and Synchrotron Radiation

Polyurethane (PU) and polystyrene (PS) films were functionalized by ultraviolet (UV) or selective synchrotron radiations (SR) in the presence of reactive gases. The UV-PU results were compared with lowpressure plasma treatments of the same films. Oxygen or acrylic acid vapours (AA) were used as reactive gases. X-ray photoelectron spectroscopy measurements of UV modified films in the presence of oxygen or AA matched the RF-plasma treatments results. It is shown that COO and C=O functional groups were incorporated at the polymer surface efficiently with both methodologies. In addition, near-edge X-ray absorption fine structure showed that a thin film of poly(acrylic acid) is formed over the PU and PS films during the UV irradiation in the presence of AA vapours. These results resemble previous AA low-power plasma treatments. PU and PS films were also selectively functionalized by SR using oxygen as reactive gas. Surface concentrations of COO and C=O functional groups were enhanced by C_1s → σ* _C–C excitation after irradiation and oxygen introduction. This efficient surface functionalization was clearly observed in PS films which do not have CO and COO groups in their molecular structure. Excitations involving transitions to π* orbital (π*_C=C, π*_C=O) led to much lower functionalization efficiency. The SR results can be explained by taking into account previous photon stimulated ion desorption studies of polymers. SR results may open new ways to functionalize polymer surfaces selectively and efficiently.     

On the Plasma Chemistry of an RF Discharge Containing Aluminium Tri‐Isopropoxide Studied by FTIR Spectroscopy

In Ar and Ar/N₂ radio frequency (RF) discharges with admixtures of aluminium tri‐isopropoxide (ATI) the fragmentation of this metal‐organic precursor was studied by means of Fourier Transform Infrared (FTIR) spectroscopy using an optical long path cell providing an optical length of l = 17.2 m. The experiments were performed in an asymmetric capacitively coupled process plasma at a frequency of f = 13.56 MHz and at pres‐sure values in the range of p = 1–10.5 Pa. The discharge power was chosen between P = 10–100 W. Using FTIR spectroscopy the evolution of the concentrations of ATI and of six stable molecules, CH₄, C₂H₂, C₂H₄, C₂H₆, CO and HCN, was monitored under flowing conditions at gas flows of Φ_total = 0.5–14.5 sccm in the discharge. The concentrations of the reaction products were measured tobe between 2 x 10¹² molecules cm^–3 as e.g. found for C₂H₄and C₂H₆, and 5 x 10¹³ molecules cm^–3, as e.g. in the case of CO. In the plasma a complete dissociation of the precursor ATI was found at a power value of about P = 80 W independent on the admixture of Ar or N₂. The fragmentation efficiency (F_E) of the reaction products which originate from the ATI molecules ranges between 0.2 and 4 x 10¹⁶ molecules J^–1 while the fragmentation rate (F_R) reached up to 2.5 x 10¹⁸ molecules s^–1. The multi component detection ability of the spectrometer served to analyse the carbon balance of the by‐product formation. For all experiments, the carbon balance never exceeded 25%. Therefore, in the plasmas the majority of the provided carbon is most likely deposited at the reactor walls or forms dust particles or higher molecular C_xH_y. The conversion efficiencies (C_E) of the produced molecular species ranges between 0.1 x 10¹⁵ molecules J^–1 for C₂H₄ and 5 x 10¹⁵ molecules J^–1 for C₂H₆ depending on the discharge conditions of the RF plasma. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

PECVD of Carbon Nanostructures in Hydrocarbon‐Based RF Plasmas

Different aspects of the plasma‐enhanced chemical vapor deposition of various carbon nanostructures in the ionized gas phase of high‐density, low‐temperature reactive plasmas of Ar+H₂+CH₄ gas mixtures are studied. The growth techniques, surface morphologies, densities and fluxes of major reactive species in the discharge, and effects of the transport of the plasma‐grown nanoparticles through the near‐substrate plasma sheath are examined. Possible growth precursors of the carbon nanostructures are also discussed. In particular, the experimental and numerical results indicate that it is likely that the aligned carbon nanotip structures are predominantly grown by the molecular and radical units, whereas the plasma‐grown nanoparticles are crucial components of polymorphous carbon films. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Diagnostics of a Compact Discharge-Pumped XeCl Laser with BCl3 Halogen Donor

The results of a comprehensive study of a compact UV-preionized XeCl laser are presented. The subjects of this study were: discharge voltage and current measurements, dye laser probing of the active medium, and the mass spectrometry of gas mixture degradation products. It is shown that the gas lifetime was significantly improved when the laser was operated with BCl₃ as a halogen donor instead of commonly used HCl. By the dye laser absorption and gain probing, the temporal and spatial dependences of the densities for several plasma components, Ne*, Xe*, Xe⁺*, Cl^–, XeCl* and of ground state boron atoms were measured. Some aspects of plasma kinetics for uniform and constricted phases of the discharge are discussed. By the mass spectrometry of gas mixture degradation products on long-term operation of the laser device several gaseous (N₂, O₂, CO₂, H₂O, C₂H₄) and solid (NiCl₂, H₃BO₃) products were detected in the laser chamber. NH₄Cl was determined to be a stable fraction of the deposits on optics surfaces. The reasons for the improvement of gas lifetime for BCl₃-containing gas mixtures are discussed.     

Antibacterial effect of silver modified TiO<Subscript>2</Subscript>/PECVD films

This paper deals with photocatalytic activity of silver treated TiO₂ films. The TiO₂ films were deposited on glass substrates by plasma enhanced chemical vapor deposition (PECVD) in a vacuum reactor with radio frequency (RF) low temperature plasma discharge in the mixture of oxygen and titanium isopropoxide vapors (TTIP). The depositions were performed under different deposition conditions. Subsequently, the surface of TiO₂ films was modified by deposition of silver nanoparticles. Photocatalytic activity of both silver modified and unmodified TiO₂ films was determined by decomposition of the model organic matter (acid orange 7). Selected TiO₂ samples were used for tests of antibacterial activity. These tests were performed on Gram-negative bacteria Escherichia coli. The results clearly proved that presence of silver clusters resulted in enhancement of the photocatalytic activity, which was up to four times higher than that for pure TiO₂ films.     

Gas by-products of CF3I under AC partial discharge

This paper presents the decomposition by-products of trifluro-iodo-methane and their relative proportions in the gas phase under the occurrence of partial discharge. The experiment was performed in the presence of water vapor from 250 to 400 ppm under a non-uniform electric field configuration. The experimental results reveal that the by-products of C₂F₆, C₂F₄, C₂F₅I with the amount of 1300, 200, and 55 (CH₃I) ppm, respectively, were produced for a cumulative charge of 161 mC. Other by-products, such as C₃F₈, CHF₃, C₃F₆ CH₃I were obtained at less than 30 ppm C₂F₆ was the dominant gas by-product of trifluro-iodo-methane suffering partial discharge.     

Preparation of thin Si:H films in an inductively coupled plasma reactor and analysis of their surface roughness

An important concern in the deposition of Si:H films is to obtain smooth surfaces. Herein, we deposit the thin Si:H films using Ar-diluted SiH₄ as feedstock gas in an inductively coupled plasma reactor. And we carry a real-time monitor on the deposition process by using optical emission spectrum technology in the vicinity of substrate and diagnose the Ar plasma radial distribution by Langmuir probe. Surface detecting by AFM and surface profilometry in large scale shows that the thin Si:H films have small surface roughness. Distributions of both the ion density and the electron temperature are homogeneous at h = 0.5 cm. Based on these experimental results, it can be proposed inductively coupled plasma reactor is fit to deposit the thin film in large scale. Also, Ar can affect the reaction process and improve the thin Si:H films characteristics.