Carbon-plasma produced in vacuum by 532 nm-3 ns laser pulses ablation

A study of VIS laser ablation of graphite, in vacuum, by using 3 ns Nd:YAG laser radiation is reported. Nanosecond pulsed ablation gives an emission mass spectrum attributable to C_n neutral and charged particles. Mass quadrupole spectroscopy, associated to electrostatic ion deflection, allows estimation of the velocity distributions of several of these emitting species within the plume as a function of the incident laser fluence. Time gated plume imaging and microscopy measurements have been used to study the plasma composition and the deposition of thin carbon films. The multi-component structure of the plume emission is rationalized in terms of charge state, ions temperature and neutrals temperature. A special regard is given to the ion acceleration process occurring inside the plasma due to the high electrical field generated in the non-equilibrium plasma conditions. The use of nanosecond laser pulses, at fluences below 10 J/cm², produces interesting C-atomic emission effects, as a high ablation yield, a high fractional ionization of the plasma and presence of nanostructures deposited on near substrates.     

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.     

Deposition of conductive TiN shells on SiO<Subscript>2</Subscript> nanoparticles with a fluidized bed ALD reactor

Conductive TiN shells have been deposited on SiO₂ nanoparticles (10–20 nm primary particle size) with fluidized bed atomic layer deposition using TDMAT and NH₃ as precursors. Analysis of the powders confirms that shell growth saturates at approximately 0.4 nm/cycle at TDMAT doses of >1.2 mmol/g of powder. TEM and XPS analysis showed that all particles were coated with homogeneous shells containing titanium. Due to the large specific surface area of the nanoparticles, the TiN shells rapidly oxidize upon exposure to air. Electrical measurements show that the partially oxidized shells are conducting, with apparent resistivity of approximately ~11 kΩ cm. The resistivity of the powders is strongly influenced by the NH₃ dose, with a smaller dose giving an order-of-magnitude higher resistivity.     

Carbon nitride films by RF plasma assisted PLD: Spectroscopic and electronic analysis

Carbon nitride (CNx) thin films have been grown on Si 〈1 0 0〉 by 193 nm ArF ns pulsed laser ablation of a pure graphite target in a low pressure atmosphere of a RF generated N₂ plasma and compared with samples grown by PLD in pure nitrogen atmosphere. Composition, structure and bonding of the deposited materials have been evaluated by X-ray photoelectron spectroscopy (XPS), and Raman scattering. Significant chemical and micro-structural changes have been registered, associated to different nitrogen incorporation in the two types of films analyzed. The intensity of the reactive activated species is, indeed, increased by the presence of the bias confined RF plasma, as compared to the bare nitrogen atmosphere, thus resulting in a different nitrogen uptake in the growing films. The process has been also investigated by some preliminary optical emission studies of the carbon plume expanding in the nitrogen atmosphere. Optical emission spectroscopy reveals the presence of many excited species like C⁺ ions, C atoms, C₂, N₂; and CN radicals, and N₂⁺ molecular ions, whose relative intensity appears to be increased in the presence of the RF plasma. The films were also characterised for electrical properties by the “four-probe-test method” determining sheet resistivity and correlating surface conductivity with chemical composition.     

Compositional analysis of ferroelectric films coated with carbon layer using laser-induced plasmas spectroscopy

An experimental investigation of the effect of different thickness of carbon layer coated on ferroelectric films on the atomic emission intensity using laser-induced plasmas spectroscopy technique with charge-coupled device (CCD) experimental system has been conducted. The experimental results show that the intensity of the spectra emitted with the carbon layer thickness of 15 μm is much higher than that of pure ferroelectric films. By using this best experimental condition, the atomic concentration ratios of ferroelectric films are evaluated by rationing the integrated intensities of selected spectral emission lines of the plasma produced from the films. And the experimental results show that N_La/N_Co and N_Sr/N_Co atomic concentration ratios are almost in agreement with the corresponding values obtained by traditional compositional analysis techniques of inductively coupled plasma (ICP).     

Optical emission spectroscopy investigation of sputtering discharge used for SiOxNy thin films deposition and correlation with the film composition

The r.f. discharge of sputtering silicon target using argon-oxygen-nitrogen plasma was investigated by optical emission spectroscopy. Electronic temperature (T_e) and emission line intensity were measured for different plasma parameters: pressure (from 0.3 to 0.7 Pa), power density (0.6-5.7 W cm⁻²) and gas composition. At high oxygen concentration in the plasma, both T_e and the target self-bias voltage (V_b) steeply decrease. Such behaviour traduces the target poisoning phenomenon. In order to control the deposition process, emission line intensity of different species present in the plasma were compared to the ArI (λ = 696.54 nm) line intensity and then correlated to the film composition analysed by Rutherford Backscattering Spectroscopy.     

Electrical and electronic properties of nitrogen doped amorphous carbon (a-CNx) thin films

Nitrogen-doped amorphous carbon thin films (a-CN_x) were prepared on silicon substrate by pulsed laser deposition process using methane (CH₄) and nitrogen (N₂) as source gas. The electrical properties of a-CN_x films changes with nitrogen concentration in the film structure. The intensity ratio of the D and G peak (I_D/I_G) increases with higher nitrogen concentration, which means that sp²-clusters were formed in these films and is responsible for the enhancement of conductivity of the a-CN_x films. We observed that the amorphous carbon (a-C) films becoming more graphitic in nature yielding higher conductivity/lower resistivity with increase of nitrogen concentration. Electron field emission result shows that the emission current density enhances with nitrogen doping that indicates the useful in electron field emission devices application.     

A comparative study of the physical properties of Sb2S3 thin films treated with N2 AC plasma and thermal annealing in N2

As-deposited antimony sulfide thin films prepared by chemical bath deposition were treated with nitrogen AC plasma and thermal annealing in nitrogen atmosphere. The as-deposited, plasma treated, and thermally annealed antimony sulfide thin films have been characterized by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy, scanning electron microscopy, atomic force microscopy, UV-vis spectroscopy, and electrical measurements. The results have shown that post-deposition treatments modify the crystalline structure, the morphology, and the optoelectronic properties of Sb₂S₃ thin films. X-ray diffraction studies showed that the crystallinity of the films was improved in both cases. Atomic force microscopy studies showed that the change in the film morphology depends on the post-deposition treatment used. Optical emission spectroscopy (OES) analysis revealed the plasma etching on the surface of the film, this fact was corroborated by the energy dispersive X-ray spectroscopy analysis. The optical band gap of the films (E_g) decreased after post-deposition treatments (from 2.36 to 1.75 eV) due to the improvement in the grain sizes. The electrical resistivity of the Sb₂S₃ thin films decreased from 10⁸ to 10⁶ Ω-cm after plasma treatments.     

Pulsed laser ablation of SiC in a nitrogen atmosphere: formation of CN

Optical emission lines from the plasma generated by a laser ablation process have been investigated to gather information on the nature of the chemical species present. In particular, the experiments were carried out during the laser ablation of a ceramic sintered SiC target, both in vacuum and in presence of controlled nitrogen atmosphere. Time integrated and spatially resolved emission spectra are dominated by the atomic emission lines from silicon and carbon species, either neutral, or singly ionized. When the ablation process was carried out in a nitrogen gas background direct evidence of the formation of the CN molecular specie was found. Fast photography imaging of the expanding plume revealed the formation of a shock wave at nitrogen pressure above 13.3 Pa, with the consequent heating of the shocked region and enhancement of the kinetics of ionization and excitation. Since the C₂ specie was absent, a CN formation mechanism involving atomic carbon and nitrogen in the presence of a shock wave is suggested. PACS 52.38.Mf; 52.50.Jm, 47.40.-x     

Laser ablation time-of-flight mass spectrometry (LA-TOF-MS) of “nitrogen doped diamond-like carbon (DLN) nano-layers”

Nitrogen-doped diamond-like carbon (DLC) layers (a-C:H:N, N-DLC or DLN) were prepared by the plasma-enhanced chemical vapor deposition (PECVD) technique, using a RF capacitive discharge (13.56 MHz), at low pressures (20 Pa), produced from a mixture of methane, nitrogen and hexamethyldisiloxane (HMDSO), deposited on single-crystalline silicon wafers placed on steel samples. The films, of differing deposition times, were subjected to laser ablation time-of-flight (LA-TOF) mass spectrometric measurements, using different commercial instrumentation to characterize their structures. The analysis of mass spectra was made and the following positively singly charged species were detected and identified: C_n⁺ (n=4–30), Si_n⁺ (n=2, 3), Si_nH⁺ (n=2, 3), SiOK⁺, Si₃H₄⁺, Si₂N⁺, Si₂NH₂⁺, and Si₃C⁺. The later three species could reflect the presence of nitrogen–silica and carbon–silica chemical bonds in the structure of the DLN layer. The stoichiometry of all species was confirmed by isotopic pattern simulation. In the negative detection mode, the C_n⁻ (n=2–12) clusters were observed. The findings are discussed in the light of the current research concerning analysis of the DLN thin layers and it is concluded that namely Si₂N⁺, Si₂NH₂⁺ and Si₃C⁺ species are reflecting the chemical structure of the DLN layer. LA-TOF-MS was found useful supplementary method for the characterization of DLN nano-layers.     

Modelling the effects of nitrogen doping on the carbon nanofiber growth via catalytic plasma‐enhanced chemical vapour deposition process

An analytical model is developed to describe the effects of nitrogen doping on the growth of the carbon nanofibers (CNFs) and to elucidate the growth mechanism of nitrogen‐contained carbon nanofibers (N‐CNFs) on the catalyst substrate surface through the plasma‐enhanced chemical vapour deposition (PECVD) process. The analytical model accounts for the charging of CNFs, kinetics of all plasma species (electrons, ions, and neutrals) in the reactive plasma, generation of carbon species on the catalyst nanoparticle surface due to dissociation of hydrocarbons, CNF growth due to diffusion and precipitation of carbon species, and various other processes. First‐order differential equations have been solved for glow discharge plasma parameters for undoped CNFs (CNF growth in C₂H₂/H₂ plasma) and nitrogen‐doped CNFs (N‐CNF growth in C₂H₂/NH₃ plasma). Our investigation found that nitrogen‐doped CNFs exhibit lower tip diameters and smaller heights compared to the undoped CNFs. In addition, we have estimated that nitrogen‐doped CNFs have more enhanced field emission characteristics than the undoped CNFs. Moreover, we have also observed that N‐CNFs' growth rate increases and tip diameter decreases as the C₂H₂/NH₃ gas ratio decreases. The theoretical results of the present investigation are consistent with the existing experimental observations.     

Optical emission spectroscopy during fabrication of indium-tin-oxynitride films by RF-sputtering

Indium-tin-oxide (ITO) and indium-tin-oxynitride (ITON) films have been deposited on glass by rf-sputtering from an ITO target, using Ar plasma and N₂ plasma, respectively, and different rf-power. Optical emission spectroscopy (OES) was employed to identify the species present in the plasma and to correlate them with the properties of the ITO and ITON thin films. Emission lines of ionic In could only be detected in N₂ plasma, whereas in the Ar plasma additional lines corresponding to atomic In and InO, were detected. The deposition rate of thin films was correlated with the In species, rather than the nitrogen species, emission intensity in the plasma. The higher resistivity and lower carrier concentration of the ITON films, as compared to the respective properties of the ITO films, were attributed to the incorporation of nitrogen, instead of oxygen, in the ITON structure.     

Langmuir probe and spectroscopic studies of RF generated helium-nitrogen mixture plasma

This paper reports the effect of helium percentage variation in a capacitive RF helium-nitrogen mixture plasma on various plasma parameters and concentration of nitrogen active species (N₂(C³Π _u) and N₂ ⁺(B²Σ _u ⁺)). Langmuir probe is used for determination of electron energy distribution functions, effective electron temperature, plasma potential and electron density. Optical emission spectroscopy is used for determination of electron temperature from Boltzmann's plot of He–I lines and the relative changes in the concentration of active species by measuring the emission intensities of nitrogen (0-0) bands of the second positive and the first negative systems. The results demonstrate that electron temperature, electron density and concentration of active species increase significantly with increase in helium percentage in the mixture and RF power.     

Systematic trends in the radiative emission rates for low- and medium-Z elements in high-temperature plasmas

The power radiated by an optically thin, low-density (N_e ≤ 10¹⁴ electrons/cm³) plasma has been calculated for the electron temperature range 1–10⁶ eV taking into account resonance line emission, direct recombination radiation, dielectronic recombination radiation, and bremsstrahlung from the ions of a given element. The ionization structure has been determined by using a corona equilibrium model in which collisional ionization and inner-shelled excitation followed by autoionization are balanced by direct radiative and dielectronic recombination. Based on the results for respresentative elements from carbon through nickel, graphs are presented of the maximum radiated power, the maximum emission temperature, and the mean charge at the maximum for each shell as functions of the atomic number Z. Assuming that the maximum emission temperature can be achieved, aluminum and iron are predicted to be the most efficient K-shell radiators for Z ≤28.     

射频激发热丝化学气相沉积制备硅薄膜过程中光发射谱的研究

采用射频(rf)激发,在热丝化学气相沉积(HWCVD)制备微晶硅薄膜的过程中产生发光基元,测量了rf激发HWCVD (rf-HWCVD)的光发射谱,比较了相同工艺条件下rf-HWCVD和等离子体增强CVD(PECVD)的光发射谱,分析了rf功率、热丝温度和沉积气压对rf-HWCVD光发射谱的影响.结果表明,在射频功率<0.1W/cm²时,rf-HWCVD发射光谱反映了HWCVD高的气体分解效率和高浓度原子氢的特点,能够解释气压变化与微晶硅薄膜微结构的关系,是研究HWCVD气相过程的有 关键词： HWCVD OES 微晶硅     

Optical emission spectroscopy of Ar-N2 mixture plasma

Optical emission spectroscopy measurements are presented to characterize the different excitation and ionization processes of both atomic and molecular species in Ar-N₂ mixture plasma under different discharge conditions. Particularly, the emission intensities of nitrogen (0-0) band of second positive system at 337.1 nm and (0-0) band of first negative systems at 391.4 nm are used to determine the dependence of their radiative states on argon fraction in the mixture. It is observed that the addition of argon gas influences the radiative states differently due to their different populating mechanisms. The results demonstrate that the addition of argon to nitrogen plasma remarkably enhance the population of N₂(C³Π_u) radiative state through Penning excitation involving argon metastable states. The electron temperature is determined from Ar-I spectral line intensities, using Boltzmann's plot method and is found to depend on argon fraction in the mixture.     

The oxidation of carbon monoxide on polycrystalline rhodium under knudsen conditions: II. Reaction with nitrogen monoxide

The reaction between carbon monoxide and nitrogen monoxide on a polycrystalline rhodium ribbon under stationary conditions is followed by mass spectrometry. In the temperature range 300 to 1100 K the ratio of the partial pressures of the reactants varies between 0.1 < p_NO/p_CO < 100 at values of the total pressure in the reactor from 10^?4 to 10^?5 Torr. The results can be interpreted qualitatively by a simple elementary reaction sequence. Simulation using literature values of the kinetic constants leads to semi-quantitative agreement with experimental results. No isothermal oscillations of the reaction rate could be observed under the stated conditions.     

Formation of silicon carbide in silicon substrates during CF4/H2 dry etching

Silicon specimens which had been reactive ion etched in CF₄/X%H₂ (0≤ X ≤40) and subsequently air exposed have been characterised by X-ray photoelectron emission spectroscopy. Angular rotation was used to study films deposited by the plasma process onto the Si surface. In agreement with previous studies it is found that plasma exposure of Si specimens leads to the deposition of a fluorocarbon film. An intriguing new finding was the discovery of subsurface silicon carbide. The existence of this carbide layer was found to be independent of gas composition from 0–40% H₂ for a one-minute plasma exposure. Helium ion channeling studies of the same specimens show Si near-surface disorder. A silicon-carbide formation mechanism is suggested according to which carbon is deposited below the Si surface by the bombardment of carbon containing ions, thus enabling silicon-carbon bonding.     

Temperature Distributions Across the Plasma Layer of Planar Low Pressure Microwave Plasmas — A Comparative Investigation by Optical Emission Spectroscopy

Nowadays low temperature non-equilibrium plasmas received considerable attention in very different fields of plasma processing. The subject of the present paper is the comparative measurement of neutral gas temperature and optical excitation temperature to analyze the temperature distributions across the plasma layer of H₂ non-equilibrium plasmas (p = 0.2 – 1.5 kPa) with small admixtures of hydrocarbons in a novel planar microwave plasma source (2.45 GHz) used for plasmachemical deposition purposes by means of optical emission spectroscopy. Typical microwave power flux densities into the plasma lie within a range of 2 W cm^?2 to 20 W cm^?2. Results of neutral gas temperature measurements derived from H_α line Doppler profiles are compared with rotational temperatures of H₂ and N₂ molecules. The neutral gas temperature (800–1700 K) corresponds to the rotational temperature of the H₂ molecules (Fulcher band, R 0–0 branch) but shows a more distinct spatial gradient. The rotational temperature of admixtured N₂ molecules (2000–3000 K) is much more higher although Boltzmann distribution was ensured. The spatially resolved measured excitation temperature (1–3 eV) determined with the help of line intensity ratios of admixtured Ar well agrees with Langmuir probe measurements. The reported measurements as a whole demonstrate the feasibility of comparative investigations of different optically determined temperatures for expressive characterization of low pressure microwave plasmas.     

Carbon monoxide and carbon dioxide interaction with tantalum

The adsorption of carbon monoxide and carbon dioxide on tantalum and the dissolution of these gases in the adsorbent at T ? 300 K have been studied. The flash-filament method (FFM) in a monopole mass-spectrometer and a field emission microscopy was used in the same apparatus. Carbon monoxide and carbon dioxide dissociate on the tantalum surface, carbon monoxide being desorbed in both cases during the flash. The desorption curves of CO reveal three different binding states: two of them (α and $\text{}\text{?}$gb₁) for the adsorbed particles whereas the high temperature desorption state relates to the adsorbate dissolved in the metal, For the $\text{}\text{?}$gb₁ state of CO the activation energy, the pre-exponential factor and the kinetic order in the kinetic equation of desorption have been estimated. They turned out to be E = 110 kcal/mol, C = 3 × 10¹²sec^?1, and ν = 1. The activation energy of diffusion for CO in tantalum and the energy of outgassing for the metal were found to be 9.4 and 49 kcal/mole, respectively.