In a distributed antenna array (DAA) reactor, microwave H 2 plasmas with admixtures of 2.5% CH 4 and 1% CO 2 used for the deposition of nanocrystalline diamond films have been studied by infrared absorption and optical emission spectroscopy (OES) techniques. The experiments were carried out in order to analyze the dependence of plasma chemical phenomena on power and pressure at relatively low pressures, up to 0.55 mbar, and power values, up to 3 kW. The evolution of the concentration of the methyl radical, CH 3 , and of five stable molecules, CH 4 , CO 2 , CO, C 2 H 2 and C 2 H 6 , was monitored in the plasma processes by in situ infrared laser absorption spectroscopy using lead salt diode lasers (TDL) and external-cavity quantum cascade lasers (EC-QCL) as radiation sources. OES was applied simultaneously to obtain complementary information about the degree of dissociation of the H 2 precursor gas and of its gas temperature. The experimental results are presented in two separate parts. In Part I, the present paper, the measurement of the gas (T gas ), rotational (T rot ) and vibrational (T vib ) temperatures of the various species in the complex plasma was the main focus of interest. To achieve reliable values for the gas temperature inside and outside the plasma bulk as well as for the rotational and vibrational temperatures in the plasma hot zones, which are of great importance for calculation of species concentrations, five different methods based on the emission and absorption spectroscopy data of H 2 , CH 4 , CH 3 and CO have been used. In these, line profile analysis has been combined with Boltzmann plot methods. Based on the wide tuning range of the EC-QCL, a variety of CO lines in the ground and three excited states was measured enabling extensive temperature analysis providing new insight into the energetic aspects of this multi-component plasma. Depending on the different plasma zones the gas temperature was found to range between about 360 and 1000 K inside the DAA reactor. In Part II, based on detailed concentration measurements general plasma chemical aspects will be analyzed and discussed.

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+ ion which has been in a range of 650–900 K 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:The considerably higher power and wider frequency coverage available from quantum cascade lasers (QCLs) in comparison to lead salt diode lasers has led to substantial advances when QCLs are used in pure and applied infrared spectroscopy. Furthermore, they can be used in both pulsed and continuous wave (cw) operation, opening up new possibilities in quantitative time resolved applications in plasmas both in the laboratory and in industry as shown in this article. However, in order to determine absolute concentrations accurately using pulsed QCLs, careful attention has to be paid to features like power saturation phenomena. Hence, we begin with a discussion of the non-linear effects which must be considered when using short or long pulse mode operation. More recently, cw QCLs have been introduced which have the advantage of higher power, better spectral resolution and lower fluctuations in light intensity compared to pulsed devices. They have proved particularly useful in sensing applications in plasmas when very low concentrations have to be monitored. Finally, the use of cw external cavity QCLs (EC-QCLs) for multi species detection is described, using a diagnostics study of a methane/nitrogen plasma as an example. The wide frequency coverage of this type of QCL laser, which is significantly broader than from a distributed feedback QCL (DFB-QCL), is a substantial advantage for multi species detection. Therefore, cw EC-QCLs are state of the art devices and have enormous potential for future plasma diagnostic studies.

A laboratory scale plasma nitriding monitoring reactor (PLANIMOR) has been designed to study the basics of active screen plasma nitriding (ASPN) processes. PLANIMOR consists of a tube reactor vessel, made of borosilicate glass, enabling optical emission spectroscopy (OES) and infrared absorption spectroscopy. The linear setup of the electrode system of the reactor has the advantages to apply the diagnostic approaches on each part of the plasma process, separately. Furthermore, possible changes of the electrical field and of the heat generation, as they could appear in down-scaled cylindrical ASPN reactors, are avoided. PLANIMOR has been used for the nitriding of steel samples, achieving similar results as in an industrial scale ASPN reactor. A compact spectrometer using an external cavity quantum cascade laser combined with an optical multi-pass cell has been applied for the detection of molecular reaction products. This allowed the determination of the concentrations of four stable molecular species (CH4, C2H2, HCN, and NH3). With the help of OES, the rotational temperature of the screen plasma could be determined.

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