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The active screen plasma nitrocarburizing technology is an improvement of conventional plasma nitrocarburizing by providing a homogeneous temperature distribution within the workload and reducing soot formation. In this study, an industrial-scale active screen (AS) made of carbon-fibre-reinforced carbon serves as the cathode as well as the carbon source for the plasma-chemical processes taking place. The pulsed dc discharge was maintained at a few mbar of pressure while simultaneously being fed with a mixed gas flow of hydrogen and nitrogen ranging from 10 to 100 slh. Using in situ infrared laser absorption spectroscopy with lead salt tuneable diode lasers and external-cavity quantum cascade lasers, the temperatures and concentrations of HCN, NH3, CH4, C2H2, and CO have been monitored as a function of pressure and total gas flow. To simulate industrial treatment conditions the temperature of the sample workload in the centre of the reactor volume was kept at 773 K by varying the plasma power at the AS between 6 and 8.5 kW. The resulting spectroscopically measured temperatures in the plasma agreed well with this value. Concentrations of the various species ranged from 6 × 1013 to 1 × 1016 cm−3 with HCN being the most abundant species. [ABSTRACT FROM AUTHOR]

Low-pressure pulsed dc H2–N2 plasmas with admixtures of CH4 or CO2 used for conventional (CPN) and active screen plasma nitriding (ASPN) were studied by infrared absorption and optical emission spectroscopy (OES) techniques. The experiments were performed in two modes: (i) the plasma at an internal model probe, driven by a bias voltage operated only, representing a CPN approach, and (ii) the screen plasma operated only, which corresponds to an ASPN experiment. Combining in situ tunable diode laser absorption spectroscopy with ex situ Fourier transform infrared spectroscopy the evolution of the concentrations of the methyl radical and of eight stable molecules, C2H2, CH4, C2H4, CO, CO2, NH3, HCN and H2O was monitored. The degree of dissociation of the carbon-containing precursor molecules varied between 40% and 98%. The methyl radical concentration was found to be in the range 1011–1012 molecules cm−3. By analysing the development of molecular concentrations with changes in gas mixtures and plasma power values, it was found that (i) C2H2, HCN and NH3 were the main products of plasma conversion in the case of methane admixture and (ii) CO, HCN and NH3 in the carbon dioxide case. The fragmentation efficiencies of methane and carbon dioxide (RF (CH4) ≈ (0.5–4) × 1016 molecules J−1, RF (CO2) ≈ (0.5–3.4) × 1016 molecules J−1) and the respective conversion efficiencies to the product molecules (RC (product) ≈ 1013–1015 molecules J−1) were determined for different gas mixtures and plasma power values. With the help of OES the rotational temperature of the screen plasma could be determined, which increased with power from 600 to 850 K. Also with power the ionic component of nitrogen molecules, i.e. the intensity of the -(0–0)-band, increased strongly in relation to the intensity of the neutral component, represented by the N2-(0–2)-band. [ABSTRACT FROM AUTHOR]

Microwave (MW) H2 plasmas with small admixtures of CH4 and/or B2H6 used for doped diamond deposition have been studied by infrared absorption and optical emission spectroscopy (OES) techniques. The experiments were carried out in order to analyze the dependence of the plasma chemistry on several parameters in the MW discharges, such as power, pressure and gas mixture, at relatively high pressures, i.e. up to 300 mbar, and power values, i.e. up to 4 kW. The evolution of the concentrations of five stable molecules, CH4, C2H2, C2H4, C2H6 and B2H6, was monitored in the plasma processes by in situ infrared tunable diode laser absorption spectroscopy. OES was used simultaneously to gather complementary information about the concentration of the boron atom. One target was the determination of the precursors' fragmentation rates and the conversion rates to the molecular reaction products. The analysis of correlations between the power and pressure of the plasma and molecular concentrations, and the differences found with CH4 and B2H6 admixtures were another focus of interest. The degree of dissociation of the carbon containing precursor molecule CH4 varied between 35% and 75%, while the decomposition of diborane, the boron precursor, varied between 85% and 97%. By analyzing the development of the molecular concentrations with changes of gas mixtures, pressure and plasma power values, it was found that (i) C2H2 is the most abundant reaction product in the plasma in the case of methane admixture and (ii) the boron atom concentration depends strongly on the presence of hydrocarbons in the plasma. The fragmentation efficiencies of methane and of diborane (RF(CH4) ≈ (1–2) × 1015 molecules J−1, RF(B2H6) ≈ (0.4–1.4) × 1013 molecules J−1) and the conversion efficiencies to the molecular products (RC(product) ≈ 1013–1015 molecules J−1) have been determined for different gas mixtures and plasma power, and pressure values. The boron atom balance, in relation to the dissociated B2H6 molecules was found to vary between 10% and 40% depending on the discharge conditions. [ABSTRACT FROM AUTHOR]

In Ar and He radio-frequency (RF) plasmas with admixtures of C2H2 and CH4 the hydrocarbon chemistry has been studied in relation to dust particle formation by means of infrared tunable diode laser absorption spectroscopy (TDLAS) combined with Fourier transform infrared (FTIR) spectroscopy. The experiments were performed in a RF capacitively coupled parallel plate reactor at a frequency of f = 13.56 MHz, a pressure of p = 0.1 mbar and a flow rate of Φ = 8 sccm of Ar or He with admixtures of 0.5 sccm C2H2 or 1 sccm CH4. The power was P = 15 W. Using TDLAS, the temporal evolution of the concentrations of the methyl radical and of four stable molecules, C2H2, CH4, C2H4 and CO, was monitored in the plasma. Simultaneously, the growth process of the dust particles was analysed by FTIR spectroscopy. The degree of dissociation of the acetylene precursor was found to be nearly constant in the range of 96% under stabilized conditions for both the Ar and He plasmas. In contrast, the degree of dissociation of the methane precursor varied between 45% and 90% depending (i) on the appearance of dust particles in the reactor volume and (ii) on the Ar or He plasma conditions. The methyl radical concentration was found to be in the range of 1011 molecules cm−3. The concentrations of all hydrocarbon species were strongly correlated with the dynamic of the dust formation. Fragmentation efficiencies of acetylene (RF (C2 H2) = 3.2 × 1016 molecules J−1) and of methane (RF (CH4) = (0.16–2.5) × 1016 molecules J−1) and conversion efficiencies to the produced hydrocarbons (RC = (0.23–8.5) × 1014 molecules J−1) could be estimated in dependence on the discharge conditions in the RF plasma. [ABSTRACT FROM AUTHOR]