Search

Low-pressure pulsed DC H2-N2 plasmas were investigated in the laboratory active screen plasma nitriding monitoring reactor, PLANIMOR, to compare the usage of two different active screen electrodes: (i) a steel screen with the additional usage of CH4 as carbon containing precursor in the feeding gas and (ii) a carbon screen without the usage of any additional gaseous carbon precursor. Applying the quantum cascade laser absorption spectroscopy, the evolution of the concentration of four stable molecular species, NH3, HCN, CH4, and C2H2, has been monitored. The concentrations were found to be in a range of 1012-1016 molecules cm-3. By analyzing the development of the molecular concentrations at variations of the screen plasma power, a similar behavior of the monitored reaction products has been found for both screen materials, with NH3 and HCN as the main reaction products. When using the carbon screen, the concentration of HCN and C2H2 was 30 and 70 times higher, respectively, compared to the usage of the steel screen with an admixture of 1% CH4. Considering the concentration of the three detected hydrocarbon reaction products, a combustion rate of the carbon screen of up to 69 mg h-1 has been found. The applied optical emission spectroscopy enabled the determination of the rotational temperature of the N2 þ ion which has been in a range of 650-900K increasing with the power in a similar way in the plasma of both screens. Also with power the ionic component of nitrogen molecules, represented by the N2+ (0-0) band of the first negative system, as well as the CN (0-0) band of the violet system increase strongly in relation to the intensity of the neutral nitrogen component, i.e., the N2 (0-0) band of the second positive system. In addition, steel samples have been treated with both the steel and the carbon screen resulting in a formation of a compound layer of up to 10 wt.% nitrogen and 10 wt.% carbon, respectively, depending on the screen material. [ABSTRACT FROM AUTHOR]

In a distributed antenna array reactor, microwave H2-CH4-CO2 plasmas with admixture of N2 used for the low-temperature deposition of nanocrystalline diamond (NCD) films are studied by in situ infrared laser absorption spectroscopy (LAS) and optical emission spectroscopy techniques. The experiments are carried out in order to analyze the dependence of temperatures and species densities as a function of the admixture of nitrogen. The evolution of the concentrations of the methyl radical (CH3), and of five stable molecules (NH3, HCN, CH4, C2H2, and CO), are monitored in the plasma processes by LAS using tunable lead salt diode lasers and external-cavity quantum cascade lasers (EC-QCL) as radiation sources. OES is performed simultaneously to obtain complementary information about (i) the degree of dissociation of H2 precursor gas, (ii) the gas temperature and therefore (iii) the density of atomic hydrogen, a key species in the chemistry of NCD deposition plasmas. The species temperatures are not significantly affected by the nitrogen addition. The concentrations of the various species are in the range between 1011 to 1015 molecules cm−3. HCN and CO are the major products in the plasma besides atomic hydrogen. The analysis of the nitrogen and carbon mass balances of the measured species shows that in addition to NH3 and HCN other nitrogen containing species are produced in the plasma which were not probed. It is shown that the formation of HCN consumes C atoms that can be provided from hydrocarbon species and from the deposition of carbon-containing films on the reactor walls, which results in a decrease of the measured densities of hydrocarbon species. [ABSTRACT FROM AUTHOR]

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]

The development of interband cascade lasers (ICLs) has made the strong C-H transitions in the 3 μm spectral region increasingly accessible. We present the demonstration of a single mode distributed feedback ICL coupled to a V-shaped optical cavity in an optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS) experiment. We achieved a minimum detectable absorption coefficient, αmin, of (7.1±0.2)×10-8 cm-1 for a spectrum of CH4 at 3.24 μm with a two second acquisition time (100 scans averaged). This corresponds to a detection limit of 3 ppb CH4 at atmospheric pressure, which is comparable to previously reported OF-CEAS instruments with diode lasers or quantum cascade lasers. The ability to frequency lock an ICL source in the important 3 μm region to an optical cavity holds great promise for future spectroscopic applications. [ABSTRACT FROM AUTHOR]

Low-pressure rf plasmas have been applied for etching of ultra-low-k SiCOH wafers using an Oxford Plasmalab System 100. In pure CF plasmas, SiCOH layers have been etched for different power values. Using quantum cascade laser absorption spectroscopy in the mid-infrared spectral range, the correlation of online and in situ measured concentrations of two etching products, CO and SiF, with the ex situ determined etching rates has been studied. The concentration of SiF was found to range between 0.6 and 1.4 × 10 molecules cm. In contrast the concentrations of CO were measured to be only about 50 % of the SiF density with 7 × 10 molecules cm in maximum. The production rate of SiF, determined from the time behavior of its concentration after plasma ignition, was found to be between 1 and 5 × 10 cm s. The etching rates varied between 2 and 7 nm s. Both parameters increase nearly linearly with the applied rf power. It was found that for power values of up to 1.1 kW, the etching rate depends nearly linearly on the in situ monitored concentrations of both etching products. Therefore, the concentration of the etching products can be directly used as a measure of the etching rate. [ABSTRACT FROM AUTHOR]

Dielectric etching plasma processes for modern interlevel dielectrics become more and more complex by the introduction of new ultra low-k dielectrics. One challenge is the minimization of sidewall damage, while etching ultra low-k porous SiCOH by fluorocarbon plasmas. The optimization of this process requires a deeper understanding of the concentration of the CF2 radical, which acts as precursor in the polymerization of the etch sample surfaces. In an industrial dielectric etching plasma reactor, the CF2 radical was measured in situ using a continuous wave quantum cascade laser (cw-QCL) around 1106.2 cm-1. We measured Doppler-resolved ro-vibrational absorption lines and determined absolute densities using transitions in the v 3 fundamental band of CF2 with the aid of an improved simulation of the line strengths. We found that the CF2 radical concentration during the etching plasma process directly correlates to the layer structure of the etched wafer. Hence, this correlation can serve as a diagnostic tool of dielectric etching plasma processes. Applying QCL based absorption spectroscopy opens up the way for advanced process monitoring and etching controlling in semiconductor manufacturing [ABSTRACT FROM AUTHOR]

The formation of carbon nanoparticles in low pressure magnetized H2/CH4 and H2/C2H2 plasmas is investigated using infrared quantum cascade laser absorption, mass spectrometry, and electrostatic probe measurements. Results showed that dust formation is correlated to the presence of a significant amount of large positively charged hydrocarbon ions. Large negative ions or neutral hydrocarbon were not observed. These results, along with a qualitative comparison of diffusion and reaction characteristic, suggest that a positive ion may contribute to the growth of nanoparticles in hydrocarbon magnetized plasmas. [ABSTRACT FROM PUBLISHER]

The wall de-excitation probability of vibrationally excited nitrogen molecules was determined using infrared (IR) titration with CO, CO2 and N2O. Gas mixtures of N2 with 0.05–0.5% of CO (CO2 or N2O) were excited by a pulsed dc discharge at p = 133 Pa in a cylindrical discharge tube. During the afterglow, the vibrational relaxation of titrating molecules was monitored in situ with quantum cascade laser absorption spectroscopy. The value of was deduced from measured vibrational relaxation times using a model of vibrational kinetics in N2. It was found that adsorption of IR tracers on the surface may increase the value of by a factor up to two, depending on the molecule and the surface material. It was demonstrated that N2O is the most inert and reliable tracer and it was used for the determination of on silica, Pyrex, TiO2, Al2O3 and anodized aluminum. Pretreatment of the silica surface by low-pressure plasma was found to have a strong effect on the vibrational de-excitation. Values of measured after O2, Ar and N2 plasma pretreatment of the same silica discharge tube were 5.7 × 10−4, 8.2 × 10−4 and 11 × 10−4, respectively. This study clearly demonstrates that the presence of adsorbed atoms and molecules on the surface may significantly alter the value of . [ABSTRACT FROM AUTHOR]

Over the past few years mid-infrared absorption spectroscopy based on quantum cascade lasers operating over the region from 3 to 12 µm and called quantum cascade laser absorption spectroscopy or QCLAS has progressed considerably as a powerful diagnostic technique for in situ studies of the fundamental physics and chemistry of molecular plasmas. The increasing interest in processing plasmas containing hydrocarbons, fluorocarbons, nitrogen oxides and organo-silicon compounds has led to further applications of QCLAS because most of these compounds and their decomposition products are infrared active. QCLAS provides a means of determining the absolute concentrations of the ground states of stable and transient molecular species at time resolutions below a microsecond, which is of particular importance for the investigation of reaction kinetics and dynamics. Information about gas temperature and population densities can also be derived from QCLAS measurements. Since plasmas with molecular feed gases are used in many applications such as thin film deposition, semiconductor processing, surface activation and cleaning, and materials and waste treatment, this has stimulated the adaptation of QCLAS techniques to industrial requirements including the development of new diagnostic equipment. The recent availability of external cavity (EC) QCLs offers a further new option for multi-component detection. The aim of this paper is fourfold: (i) to briefly review spectroscopic issues arising from applying pulsed QCLs, (ii) to report on recent achievements in our understanding of molecular phenomena in plasmas and at surfaces, (iii) to describe the current status of industrial process monitoring in the mid-infrared and (iv) to discuss the potential of advanced instrumentation based on EC-QCLs for plasma diagnostics. [ABSTRACT FROM AUTHOR]

A new method for determination of the wall de-excitation probability of vibrationally excited N2 on different surfaces exposed to low-pressure plasmas has been developed. A short dc discharge pulse of only a few milliseconds was applied to a mixture containing 0.05–1% of CO2 in N2 at a pressure of 133 Pa. Due to a nearly resonant fast vibrational transfer between N2(v) and the asymmetric ν3 mode of CO2 the vibrational excitation of these titrating molecules is an image of the degree of vibrational excitation of N2. In the afterglow, the vibrational relaxation of CO2 was monitored in situ using quantum cascade laser absorption spectroscopy. The experimental results were interpreted in terms of a numerical model of non-equilibrium vibrational kinetics in CO2–N2 mixtures. Heterogeneous relaxation was the main quenching process of N2(v) under the conditions of this study, which allowed determination of the value of from the best agreement between the experiment and the model. The new method is suitable for determination in a single plasma pulse with the discharge tube surface pretreated by a low-pressure plasma. The relaxation probability of the first vibrational level of nitrogen γ1 = (1.1 ± 0.15) × 10−3 found for Pyrex and silica is in reasonable agreement with the literature data. Using the new technique the N2(v = 1) quenching probability was measured on TiO2 surface, γ1 = (9 ± 1) × 10−3. A linear enhancement of the N2(v) wall deactivation probability with an increase in the admixture of CO2 was observed for all studied materials. In order to explain this effect, a vibrational energy transfer mechanism between N2(v) and adsorbed CO2 is proposed. [ABSTRACT FROM AUTHOR]

The introduction of room temperature continuous wave external-cavity quantum cascade lasers (EC-QCLs) with narrow linewidths has greatly facilitated high resolution spectroscopy over wide spectral ranges in the mid-infrared (MIR) region. Using the wide tuning range of an EC-QCL we have measured the absolute line strengths of many P-branch transitions of the stretching dyad of the ν 3 fundamental band of 28 SiH 4 between 2096 and 2178 cm −1 . Furthermore, the high spectral resolution available has enabled us to resolve and measure representative examples of the tetrahedral splittings associated with each component of the P-branch. The positions of these components are in excellent agreement with spherical top data system (STDS) predictions and theoretical transitions from the TDS spectroscopic database for spherical top molecules. These are the first measurements of these line strengths of 28 SiH 4 and are an example of the applicability of high-powered, widely tunable EC-QCLs to high resolution spectroscopy. [ABSTRACT FROM AUTHOR]