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The line strengths of nine Q-branch lines in the ν2 fundamental band of the methyl radical in its ground electronic state have been measured by diode laser absorption spectroscopy. The vibration–rotation spectrum of methyl was recorded in a microwave discharge in ditertiary butyl peroxide heavily diluted in argon. The absolute concentration of the radical was determined by measuring its kinetic decay when the discharge was extinguished. The translational, rotational, and vibrational temperatures, also required to relate the line strengths to the transition dipole moment, were determined from relative integrated line intensities and from the Doppler widths of the lines after allowing for instrumental factors. The line strengths of the nine Q-branch lines were used to derive a more accurate value of the transition dipole moment of this band, μ2=0.215(25) D. Improved accuracy over earlier measurements of μ2 (derived from line strengths of single lines) was obtained by integrating over the complete line profile instead of measuring the peak absorption and assuming a Doppler linewidth to deduce the concentration. In addition, a more precise value for the rate constant for methyl radical recombination than available earlier was employed. The new value of μ2 is in very good agreement with high-quality ab initio calculations. Furthermore, the ratio of the transition dipole moments of the ν2 and ν3 fundamental bands in the gas phase is now in highly satisfactory agreement with the ratio determined for the condensed phase. © 2005 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Quantum cascade lasers (QCLs) have attracted considerable interest as an alternative tuneable narrow bandwidth light source in the mid-infrared spectral range for chemical sensing. Pulsed QCL spectrometers are often used with short laser pulses and a bias current ramp similar to diode laser spectroscopy. Artefacts in the recorded spectra such as disturbed line shapes or underestimated absorption coefficients have been reported. A detailed time-resolved high-bandwidth analysis of individual pulses during a laser sweep has been performed. Quantitative results for CH absorption features around 1347 cm (7.42 μm) fell short of the expected values for reasonable operating conditions of the QCL. The origin of the artefacts using short pulses was identified to be partly of the same nature as in the case of long laser pulses. A complex combination with the tuning principle was found, leading to an apparently increased instrumental broadening (effective line width) and underestimated concentrations at low-pressure conditions. [ABSTRACT FROM AUTHOR]

Within the last decade mid-infrared absorption spectroscopy between 3 and 20 μm, known as infrared laser absorption spectroscopy (IRLAS) and based on tuneable semiconductor lasers, namely lead salt diode lasers, often called tuneable diode lasers (TDL), and quantum cascade lasers (QCL) 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, organo-silicon and boron compounds has lead to further applications of IRLAS because most of these compounds and their decomposition products are infrared active. IRLAS provides a means of determining the absolute concentrations of the ground states of stable and transient molecular species, which is of particular importance for the investigation of reaction kinetics. 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 infrared spectroscopic techniques to industrial requirements. The recent development of QCLs offers an attractive new option for the monitoring and control of industrial plasma processes as well as for highly time-resolved studies on the kinetics of plasma processes. The aim of the present article is twofold: (i) to review recent achievements in our understanding of molecular phenomena in plasmas using TDLs and (ii) to report on selected new applications of QCLs in the mid-infrared. [ABSTRACT FROM AUTHOR]

The absorption spectra of the fundamental bands of the free radicals 10B16O and 11B16O in their ground 2Σ+ states have been measured in natural abundance and at Doppler limited resolution using diode laser spectroscopy. The band origins are found to be 1915.30674(14) and 1861.92409(13) cm−1, respectively. The rotational constants for the lower states are 1.877680(22) and 1.773421(10) cm−1, which are in excellent agreement with the microwave values for B0. Assuming a linear dependence of Bv on (v+1/2) the derived value of re is 1.204552(5) A˚. [Copyright &y& Elsevier]

Many P- and R-branch lines of the fundamental bands of the 12 C 14 N and 13 C 14 N radicals in their ground ( 2 Σ + ) electronic state have been measured at high resolution by diode laser absorption spectroscopy. The radicals were generated in a 2.45 GHz planar microwave plasma in methane with varying proportions of N 2 and H 2 . From a fit to the spectra the origins of the fundamental bands of the two isotopomers were determined to be 2042.421 04(84) cm -1 and 2000.084 70(30) cm -1 . The main product detected in the plasma by diode laser spectroscopy is HCN, with concentrations about three orders of magnitude higher than CN. [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]

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]

Abstract: The kinetics of a low pressure pulsed DC discharge in dry air is experimentally studied using simultaneous measurements of the concentrations of NO and NO2 downstream the plasma region. The measurements have been performed via infrared tunable diode laser absorption spectroscopy. The gas pressure was 3.95mbar and the pulse duration and frequency range from 20μs to 3ms and from 50 to 1000Hz, respectively. The peak current was varied from 10 to 80mA. It is shown that the NO and NO2 densities depend only on the averaged current. In order to explain this feature a simplified analytical calculation has been developed which considers about 30 kinetic reactions involved in the NO x formation. The calculations lead to a fair agreement with the experimental results. [Copyright &y& Elsevier]

Relative transition probabilities of spontaneous emission in the R and P branches of the A1Π→X1Σ+ (0–0) band of BH molecule have been obtained for the first time. It was observed that measured ratios of the line strengths are in agreement with corresponding ratios of Ho¨nl–London factors. Thus, the non-adiabatic effect of perturbations is negligibly small and Ho¨nl–London formulas may be used for derivation of rovibronic population densities from measured line intensities of the (0–0)R branch of BH. The (0–0)P branch is less prospective because too much overlapping by other BH emissions cannot be avoided with the moderate resolution spectrometers usually used in plasma spectroscopy. General considerations are illustrated on the example of a low-pressure plasma of a planar microwave discharge in a H2–Ar–B2H6 (64:33:3) gas mixture (total pressure 1–2.5 mbar, power 1.2–2.4 kW). The values of the rotational temperatures obtained directly for the excited electronic-vibrational states d3Πu−, v′=2 (Td2rot(H2)) and A1Π+, v′=0 (TA0rot(BH)) and those calculated in the framework of excitation-deactivation models for the ground X1Σu+, v=0 vibronic states (TX0rot(H2) and TX0rot(BH)) have been analysed. It has been observed that TX0rot(H2) and TX0rot(BH) are in excellent agreement, while compared to these values TA0rot(BH) is noticeably higher and Td2rot(H2) is about two times lower. Thus, the simultaneous measurements of intensity distributions in the rotational structure of BH and H2 emission bands can be used as a prospective method for determination of gas temperature in non-equilibrium boron and hydrogen containing plasmas. [Copyright &y& Elsevier]

InfraRed Tunable Diode Laser Absorption Spectroscopy technique has been implemented in a H2/CH4 Micro-Wave (MW frequency f=2.45 GHz) plasma reactor dedicated to diamond deposition under high pressure and high power conditions. Parametric studies such as a function of MW power, pressure, and admixtures of methane have been carried out on a wide range of experimental conditions: the pressure up to 270 mbar and the MW power up to 4 kW. These conditions allow high purity Chemical Vapor Deposition diamond deposition at high growth rates. Line integrated absorption measurements have been performed in order to monitor hydrocarbon species, i.e., CH3, CH4, C2H2, C2H4, and C2H6. The densities of the stable detected species were found to vary in the range of 1012-1017 molecules cm-3, while the methyl radical CH3 (precursor of diamond growth under these conditions) measured into the plasma bulk was found up to 1014 molecules cm-3. The experimental densities have been compared to those provided by 1D-radial thermochemical model for low power and low pressure conditions (up to 100 mbar/2 kW). These densities have been axially integrated. Experimental measurements under high pressure and power conditions confirm a strong increase of the degree of dissociation of the precursor, CH4, associated to an increase of the C2H2 density, the most abundant reaction product in the plasma. [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 potential of an approach combining a pulsed microwave discharge with a catalytic packed bed reactor for the oxidation of volatile organic compounds (VOC) has been studied. The ignition of the plasma has been made possible by inserting ferroelectric BaTiO3 pellets inside the microwave excitator. As a test VOC molecule, acetylene (C2H2) in an amount of 200 ppm in dry air was used. The total oxidation products CO and CO2 have been monitored downstream of the plasma region by tuneable diode laser absorption spectroscopy in the infrared region. The oxidative efficiency was found to increase linearly with the pulse repetition rate. The oxidative efficiency and the CO2/CO selectivity were considerably enhanced when the catalyst was located inside the plasma region, which shows the synergetic effect of the plasma-catalyst combination. [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]

Achieving the high sensitivity necessary for trace gas detection in the midinfrared molecular fingerprint region generally requires long absorption path lengths. In addition, for wider application, especially for field measurements, compact and cryogen free spectrometers are definitely preferable. An alternative approach to conventional linear absorption spectroscopy employing multiple pass cells for achieving high sensitivity is to combine a high finesse cavity with thermoelectrically (TE) cooled quantum cascade lasers (QCLs) and detectors. We have investigated the sensitivity limits of an entirely TE cooled system equipped with an ∼0.5 m long cavity having a small sample volume of 0.3 l. With this spectrometer cavity enhanced absorption spectroscopy employing a continuous wave QCL emitting at 7.66 μm yielded path lengths of 1080 m and a noise equivalent absorption of 2×10-7 cm-1 Hz-1/2. The molecular concentration detection limit with a 20 s integration time was found to be 6×108 molecules/cm3 for N2O and 2×109 molecules/cm3 for CH4, which is good enough for the selective measurement of trace atmospheric constituents at 2.2 mbar. The main limiting factor for achieving even higher sensitivity, such as that found for larger volume multi pass cell spectrometers, is the residual mode noise of the cavity. On the other hand the application of TE cooled pulsed QCLs for integrated cavity output spectroscopy and cavity ring-down spectroscopy (CRDS) was found to be limited by the intrinsic frequency chirp of the laser. Consequently the accuracy and advantage of an absolute internal absorption calibration, in theory inherent for CRDS experiments, are not achievable. [ABSTRACT FROM AUTHOR]

We investigated the efficiency and formation mechanism of ammonia generation in recombining plasmas generated from mixtures of N2 and H2 under various plasma conditions. In contrast to the Haber-Bosch process, in which the molecules are dissociated on a catalytic surface, under these plasma conditions the precursor molecules, N2 and H2, are already dissociated in the gas phase. Surfaces are thus exposed to large fluxes of atomic N and H radicals. The ammonia production turns out to be strongly dependent on the fluxes of atomic N and H radicals to the surface. By optimizing the atomic N and H fluxes to the surface using an atomic nitrogen and hydrogen source ammonia can be formed efficiently, i.e., more than 10% of the total background pressure is measured to be ammonia. The results obtained show a strong similarity with results reported in literature, which were explained by the production of ammonia at the surface by stepwise addition reactions between adsorbed nitrogen and hydrogen containing radicals at the surface and incoming N and H containing radicals. Furthermore, our results indicate that the ammonia production is independent of wall material. The high fluxes of N and H radicals in our experiments result in a passivated surface, and the actual chemistry, leading to the formation of ammonia, takes place in an additional layer on top of this passivated surface. [ABSTRACT FROM AUTHOR]

Microwave discharges of H2 admixed with CH4 in a moderate-pressure quartz bell jar reactor used for diamond deposition are studied numerically. Special attention was devoted to high-power densities which provide the most effective way for producing high-quality diamond films. First, a one-dimensional radial model describing the coupled phenomena of chemistry, energy transfer, as well as species and energy transport along the reactor’s radial coordinate was developed. Species densities predicted with the model were compared with measurements with infrared tunable diode laser spectroscopy, resulting in validation of the model. Second, a one-dimensional axial model was used to describe the plasma flow along the reactor axis in a region between the reactor end wall and the substrate surface. This model was particularly useful for studying the plasma behavior in the vicinity of the substrate surface, where thermal and composition gradients are large. Both the radial and axial transport models are based on the same discharge model in which the plasma is described as a thermochemically nonequilibrium flow with different energy distributions for heavy species and electrons. The chemistry was described with a model containing 28 species and 131 reactions. The electron temperature, the gas temperature, and the species concentration were determined by solving a coupled set of equations. A wide range of experimental conditions used for diamond deposition was simulated, from low microwave power density (9 W cm-3, i.e., 600 W, 2500 Pa, and Tg∼2200 K) to high-power density (30 W cm-3, i.e., 2 kW, 12 000 Pa, and Tg∼3200 K). The main chemical paths were identified, and the major species, transport effects, and reaction pathways that govern diamond deposition plasmas are discussed. [ABSTRACT FROM AUTHOR]

In this paper Ar/H2/CH4 microwave discharges used for nanocrystalline diamond chemical vapor deposition in a bell-jar cavity reactor were characterized by both experimental and modeling investigations. Discharges containing 1% CH4 and H2 percentages ranging between 2% and 7% were analyzed as a function of the input microwave power under a pressure of 200 mbar. Emission spectroscopy and broadband absorption spectroscopy were carried out in the UV-visible spectral range in order to estimate the gas temperature and the C2 density within the plasma. Infrared tunable diode laser absorption spectroscopy was achieved in order to measure the mole fractions of carbon-containing species such as CH4, C2H2, and C2H6. A thermochemical model was developed and used in order to estimate the discharge composition, the gas temperature, and the average electron energy in the frame of a quasihomogeneous plasma assumption. Experiments and calculations yielded consistent results with respect to plasma temperature and composition. A relatively high gas temperature ranging between 3000 and 4000 K is found for the investigated discharge conditions. The C2 density estimated from both experiments and modeling are quite high compared with what is generally reported in the literature for the same kind of plasma system. It ranges between 1013 and 1014 cm-3 in the investigated power range. Infrared absorption measurements and model predictions indicate quite low densities of methane and acetylene, while the atomic carbon density calculated by the model ranges between 1013 and 1015 cm-3. The methane and hydrogen introduced in the feed gas are subject to a strong dissociation, which results in a surprisingly high H-atom population with mole fraction ranging between 0.04 and 0.16. Result analysis shows that the power coupling efficiency would range between 70% and 90%, which may at least explain the relatively high values obtained, as compared with those reported in the literature for similar discharges, for gas temperature and C2 population. The high H-atom densities obtained in this work would indicate that growing nanocrystalline diamond films would experience a very high etching. Simulation results also confirm that sp species would play a key role in the surface chemistry that governs the diamond growth. [ABSTRACT FROM AUTHOR]

Langmuir probe techniques have been used to study time and spatially resolved electron densities and electron temperatures in pulse-modulated hydrogen discharges in two different planar microwave reactors (ƒ[sub microwave]=2.45 GHz, t[sub pulse] = 1 ms). The reactors are (i) a standing-wave radiative slotted waveguide reactor and (ii) a modified traveling-wave radiative slotted waveguide reactor, which generate relatively large plasmas over areas from about 350 to 500 cm². The plasma properties of these reactor types are of particular interest as they have been used for basic research and for plasma processing; for example, for surface treatment and layer deposition. In the present study the pressures and microwave powers in the reactors were varied between 33 and 55 Pa and 600 and 3600 W, respectively. In regions with high electromagnetic fields, shielded Langmuir probes were used to avoid disturbances of the probe characteristic. Close to the microwave windows of the reactors both the electron density and the electron temperature showed strong inhomogeneities. In the standing-wave reactor the inhomogeneity was found to be spatially modulated by the position of the slots. The maximum value of the electron temperature was about 10 eV, and the electron density varied between 0.2 and 14 × 10[sup 11] cm[sup -3]. The steady-state electron temperature in a discharge pulse was reached within a few tens of microseconds, whereas the electron density needed some hundreds of microseconds to reach a steady state. Depending on the reactor the electron density reached a maximum between 80 and 200 µs after the beginning of the pulse. [ABSTRACT FROM AUTHOR]

• Investigation on the influence of inorganic species on wood pyrolysis. • Application of infrared laser absorption and laser-induced fluorescence spectroscopy. • Potassium leads to an overlap of cellulose and lignin decomposition with secondary reactions. • Total fluorescence intensity and exothermicity track the presence of secondary reactions. • Potassium influences the release of fluorescence-emitting species, yields and thermochemistry. The influence of inorganic species content on the slow pyrolysis of thermally thick wood particles has been investigated with the application of laser-based spectroscopic techniques. Infrared laser absorption and laser-induced fluorescence were used to characterize, on-line and in situ, the release of permanent gases (CO and CH 4) and of species emitting fluorescence, respectively. These advanced methods were combined with the continuous monitoring of mass and temperature and with off-line GC–MS analysis of the liquid fraction. The experiments were performed using spherical particles of beech, H 2 O- and HCl-washed beech, KCl-doped beech, and pine. The pyrolytic behavior of washed beech (with lower content in inorganic species) was found to resemble much closely the one of pine, rather than the one of beech, probably due to the pine low content in K. Both washed beech and pine showed a more clear separation between cellulose and lignin decomposition, being lignin decomposition, and potentially the presence of heterogeneous secondary reactions, shifted to higher temperatures. The release of species emitting fluorescence was also affected by the removal/addition of inorganic species. K was observed to catalyze the pyrolysis reaction. A strong exothermic behavior, coincident with the maximum of the TFI (tracking the release of fluorescence-emitting species -e.g. PAHs-), was observed, attributed to the presence of heterogeneous secondary (charring) reactions. Moreover, at the end of the pyrolysis process, reactions in the char matrix, enhanced by the presence of K, were detected, with no further significant mass loss or temperature gradient, leading also to the formation of fluorescence-emitting species (e.g. PAHs). Higher content in inorganic species (beech versus washed beech) resulted also in lower major carbohydrates yields and slightly higher guaiacols, syringols, and phenols yields. This indicates an enhancement of charring reactions, in good agreement with the higher exothermicity, as well as in fragmentation reactions and in lignin reactivity with higher presence of inorganic species. [ABSTRACT FROM AUTHOR]

A microwave torch in nitrogen has been designed for the evaporation of aluminium (Al) wires potentially to be used for the synthesis of aluminium nitride (AlN). The torch, created on the tip of a metallic nozzle, is compatible with vacuum conditions and can be operated in continuous mode up to atmospheric pressure. Al wires to be evaporated are fed through the axis of the nozzle. Time‐resolved photography is applied to analyse the time evolution and stability of the interaction of the Al wire with the discharge. Optical emission spectroscopy is used (a) for the determination of the gas temperature of the active discharge, which is found to be in the range 1500–3500 K depending on the experimental conditions, and (b) for the estimation of the densities of Al and N atoms in the afterglow region, which are in the range 1011–1012 and of 1013–1014 cm−3, respectively. It is found that the part of the Al wire that is directly exposed to the nitrogen torch absorbs a considerable amount of the microwave energy, supporting its evaporation. In addition, the dissociation of molecular nitrogen has to be considered as an important process of power dissipation. Further technical development of the torch is necessary for the envisaged synthesis of AlN. [ABSTRACT FROM AUTHOR]

Plasma patterning processes play a key role in modern Ultra Large Scale Integration (ULSI) device fabrication. With further scaling of device dimensions, plasma process characteristics become more and more the limiting factor in pattern minimization, not least due to parasitic effects caused by different plasma properties. Such effects are geometrical deviations in the etch profiles, the loss of critical dimensions, the undercut as well as the most critical sidewall damage while etching trenches and vias to fabricate the circuit contact and metallization system. Especially for modern dielectric materials on the base of carbon‐doped silica these drawbacks are much pronounced and worsen performance and power consumption of microelectronic devices. Finally, the charge damage of thin gate oxides during plasma processing results in reduced reliability and functionality of microelectronic devices. The complex interactions between conditions in the plasma bulk and the impacts on the wafer surface are not yet understood completely. With respect to the increasing complexity of modern semiconductor plasma etch equipment, the optimization of patterning processes using the empirical method becomes more and more impossible. This paper overviews typical challenges during plasma patterning processes in 28 nm and 22 nm technology nodes by means of today's Back‐End of Line integration schemes. Different plasma diagnostic methods provide an insight into the physical and chemical conditions of different etch chambers and their influence on process results and damaging behaviour. [ABSTRACT FROM AUTHOR]

Infrared laser absorption spectroscopy (IRLAS) and laser-induced fluorescence spectroscopy (LIF) are applied in the present study for online in-situ characterization of volatiles products in the close vicinity of a single pyrolysing wood sphere. These advanced analytical techniques are combined with online measurements of temperature and mass evolutions in order to gain further insight into the complex processes occurring during slow pyrolysis of thermally thick wood particles. Three different heating rates (5, 10, 20 °C/min) and two wood types (beech, pine) were used. Time-resolved absolute concentrations of the main permanent gases CO 2 , CO, CH 4 and H 2 O were measured applying IRLAS. From the LIF measurements the qualitative temporal release of polycyclic aromatic hydrocarbons (PAHs) could be deduced. Different behaviors regarding the release of volatiles, temperature evolution and conversion rates were observed for both wood species, which could not be ascribed only to the different content of cellulose, hemicellulose and lignin. According to the measured volatiles evolution an enhancement of heterogeneous catalytic tar cracking seemed to be present with higher heating rates for both wood types. However, the evolution of exothermicity and PAH release differed for both wood types indicating different reaction pathways. An analysis of possible reaction pathways including secondary reactions is performed taking into account all experimental findings about the in-situ composition of the volatiles and the evolution of the PAHs as well as the exothermicity. The differences in the pyrolytic behavior of both species can be related to both the chemical and physical properties of the raw materials. [ABSTRACT FROM AUTHOR]

The growth process of nanocrystalline diamond (NCD) films has been investigated and compared in two different types of microwave plasma reactors. One process occurs at high substrate temperature (1170 K) and moderate pressure (few hundreds hPa) in a bell jar (BJ) microwave cavity system working in an Ar/H 2 /CH 4 gas mixture. The second process occurs at low substrate temperature (below 670 K) in a low pressure (< 100 Pa) microwave distributed antenna array (DAA) reactor using a mixture of H 2 /CH 4 /CO 2 as feed gas. NCD films synthesized in both reactors show a grain size around 20 nm and a strong 〈110〉 fiber axis, whereas some slight disparities are observed concerning the film morphology, topography and purity. However, the growth rate is about 30 times higher in the BJ reactor. Similarities and disparities are discussed by considering possible growth mechanisms and the activation energy estimated at 3.2 and 9.0 kcal·mol − 1 for the DAA and BJ reactors, respectively, for the considered substrate temperatures. The microwave discharges were investigated by plasma modelling in case of the BJ reactor and by optical emission spectroscopy (OES) in the visible spectral range and laser absorption spectroscopy in the mid-infrared spectral range (MIR-LAS) in the case of the DAA reactor in order to determine major and key species densities as well as the gas temperature nearby the substrate. The latter is considerably higher in the BJ reactor (around 2000 K) than in the DAA reactor (below 1000 K). Thus, the plasma kinetics are mainly driven by thermal chemistry in the BJ reactor, whereas both thermal and electron driven processes govern the plasma chemistry in the DAA reactor, which results in a significantly different plasma composition close to the substrate surface. The predominance of H, C and CO species, depending on the reactor type, the comparable amount of CH 3 radicals, and the related impact on NCD growth are discussed, as well as the dissociation efficiency of both processes, with respect to the coupled microwave power. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Fuel and synthesis gases generated by thermochemical gasification of renewable biomass resources and organic waste fractions are considered to be promising for recent and future energy demands. However, the presence of tar species in the gas mixture is an economic obstacle in the commercialization of this technology. The influence of non-thermal plasma on gas phase naphthalene [ABSTRACT FROM AUTHOR]

Plasmas in interaction with surfaces are of key importance in a wide range of applications, which include materials technology, microelectronics, environmental issues, and biomedicine. The intense use of plasma technological processes demands proper plasma diagnostic techniques for monitoring, controlling and optimization purposes in industrial environments. In particular, for the improvement of the efficiency of a production process, in situ diagnostic techniques with online capabilities are favorable. From the middle of the last decade a variety of phenomena in molecular non-equilibrium plasmas in which many short-lived and stable species are produced have been successfully studied with quantum cascade laser absorption spectroscopy (QCLAS) in the mid-infrared spectral range. It has been possible to determine absolute concentrations of species, temperatures, degrees of dissociation, dynamics of reaction processes and phenomena involving plasma-surface interactions using spectroscopy, thereby providing a link with chemical and kinetic modelling of the plasma. Since quantum cascade lasers (QCLs) emit near room temperature, i.e., without the need of cryogenic cooling, very compact and robust spectroscopic instruments can be designed. This has stimulated the adaptation of infrared spectroscopic techniques to industrial requirements. Recent applications of infrared absorption spectroscopy using QCLs for in situ monitoring of plasma processes in industrial environments are reviewed. Examples which emphasize the capabilities of QCLAS as plasma diagnostic technique in industrial plasma processes will be given. (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [ABSTRACT FROM AUTHOR]

Low-pressure pulsed DC N2-H2 plasmas with admixtures of CH4 were investigated in a comparative study in two different types of reactors, (i) a cylindrical industrial scale active screen plasma nitriding (ASPN) reactor and (ii) a laboratory scale plasma nitriding monitoring reactor (PLANIMOR) with a linear electrode configuration. Applying infrared laser absorption spectroscopy (IRLAS) the evolution of the molecular concentrations of four stable molecules, CH4, HCN, NH3, and C2H2 has been monitored. The degree of dissociation of the carbon containing precursor, CH4, varied between 80 and 95%. The concentrations of the molecular reaction products have been found in a range of 1011 to 1016 molecules cm-3. By analyzing the development of the molecular concentrations at changes of the screen plasma power, the gas mixture and the admixture of CH4, a similar behavior of the monitored species depending on the varied parameters has been found in both reactors with NH3 and HCN as the main products of plasma conversion. The fragmentation efficiency of methane has been determined, decreasing from 2.4 to 0.8 × 1015 molecules J-1 with the increasing power of the screen plasmas in both reactors. With the help of optical emission spectroscopy (OES) the rotational temperature of the N+2 ions in the plasma could be determined, being in a range of 650...920 K where the rotational temperature of the screen plasma in the ASPN reactor is approximately 100 K higher than that in PLANIMOR. Also with power the ionic component of nitrogen molecules, i.e. the intensity of the N+2 -(0-0) band of the first negative system, which has been used as the reference parameter for comparing both reactors, increases strongly in relation to the intensity of the neutral component, represented by the N2-(0-0) band of the second positive system. In addition, steel samples have been treated in both the ASPN reactor and PLANIMOR leading to comparable nitriding results. (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [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 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]

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]

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) [ABSTRACT FROM AUTHOR]

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]

Abstract: Low pressure pulsed DC N2–H2 plasmas with admixtures of CH4 used for active screen plasma nitriding (ASPN) have been studied by time resolved Langmuir probe and optical emission spectroscopy (OES) techniques (f=1kHz, 60% duty cycle, p=1mbar). The temporal behavior of parameters of the electrons inside the process volume of the ASPN reactor was at the center of interest. Based on probe diagnostics the electron density and temperature as well as the plasma potential could be determined in dependence (i) on time in the discharge pulses and (ii) on parameters of the gas mixture including the N2–H2 ratio. Electron temperatures between 0.13 and 0.31V and electron densities in the order of 109 cm−3 could be measured. In addition OES has been used to receive complementary information about neutral and charged nitrogen molecules from the glow discharge between the active screen and the outer reactor wall. It was found, that the ratio of hydrogen to nitrogen content in the feed gas mixture influences the emission characteristics of the plasma at the active screen considerably, i.e. the intensity ratio of the N2 +-(0–0)- band to the N2-(0–2)-band. Another focus was the analysis of differences of the electron parameters in pure N2–H2 discharges compared to feed gas mixtures containing methane and the influence on outer electrical parameter of the ASPN reactor. Finally the results of nitriding experiments showed a correlation to the findings of the plasma diagnostic studies. [Copyright &y& Elsevier]

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]

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]

The objective of this study is to understand fundamental aspects of interactions of plasmas with catalytic surfaces. Based on this approach the reactivity of plasma treated and stimulated catalytic surfaces of TiO2 is studied by analysing the oxidation (i) of C2H2 to CO and CO2 and (ii) of CO to CO2. The inner surface of a Pyrex discharge tube is coated with TiO2 films impregnated with TiO2 nanoparticles, which provides a surface area of about 4m². In addition to the exposure of the TiO2 surface by low-pressure radio-frequency plasmas using O2, Ar or N2 (f = 13.56 MHz, p = 0.53 mbar, P = 17 W) the surfaces are stimulated by heating and UV radiation treatment. The temporal development of the concentrations of the precursor gases C2H2 or CO and of the reaction products is monitored using quantum cascade laser absorption spectroscopy, which provides multi-component detection in the mid-infrared spectral range. The C2H2 concentration was found to be nearly constant over time after a pre-treatment with Ar or N2 discharges using an initial gas mixture of 1% C2H2 in Ar. However, a strong decay of the concentration of C2H2 is observed for pure O2 plasma pre-treatment. In general, the decay is found to be nearly exponential with time constant in the order of about 10 min. The reactive adsorption of C2H2 molecules on the inner surface of the tube reactor showed a density of about 7.5 × 1012 C2H2 molecules cm-2. This behaviour demonstrates that the reaction (Oads +C2H2)TiO2 produces some adsorbed intermediates, which can be thermally or photo-catalytically oxidized to CO2. In contrast, when 1% CO in Ar is used as an initial gas mixture no adsorption processes on the TiO2 surface could be detected. An effective destruction of CO took part via photo-catalytic oxidation. [ABSTRACT FROM AUTHOR]

In Ar and Ar/N2 RF plasmas with admixtures of aluminum tri-isopropoxide (ATI) the fragmentation of this metal-organic precursor has been studied by means of infrared absorption spectroscopy (IR-AS) using an external-cavity quantum cascade laser (EC-QCL) arrangement. The experiments were performed in an asymmetric capacitively coupled reactor at a frequency of f = 13.56 MHz and a pressure of up to p = 10 Pa. The discharge power was in the range of P = 40 - 100 W. Using EC-QCLAS the evolution of the concentrations of six stable molecules, CH4, C2H2, C2H4, H2O, HCN and HNO3, has been monitored in the plasma. The concentrations of these plasma chemical products were found to be in the range of about 7 × 1012 - 2 × 1014 molecules cm-3 (© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [ABSTRACT FROM AUTHOR]

Abstract: The active screen (AS) nitriding is an advanced technology for the plasma nitriding of steel components providing a number of advantages over conventional plasma nitriding. Developed in the last decade, the AS technology has found its industrial application, however the understanding of the fundamental mechanisms and their relationship is not complete. For the first time the mid infrared tunable diode laser absorption technique in combination with the quadruple mass spectrometry has been applied in this work. In-situ diagnostics of chemical phenomena in the N2–H2 plasmas under variation of the process conditions such as H2 to N2 gas ratio, process temperature and bias activation power provided valuable information about the concentration of active nitrogen species in the vicinity of the samples'' surfaces. The thickness of the compound layer representing the nitriding efficiency was used as a response to nitriding conditions for the evaluation of selected process parameters derived from the plasma diagnostic studies. A 1:1 gas mixture of the N2–H2 process gases seems to be most effective to get thick compound layers. [Copyright &y& Elsevier]

A compact and transportable three channel quantum cascade laser system (TRIPLE Q) based on mid-infrared absorption spectroscopy has been developed for time-resolved plasma diagnostics. The TRIPLE Q spectrometer encompasses three independently controlled quantum cascade lasers (QCLs), which can be used for chemical sensing, particularly for gas phase analysis of plasmas. All three QCLs are operated in the intra-pulse mode with typical pulse lengths of the order of 150 ns. Using a multiplexed detection, a time resolution shorter than 1 μs can be achieved. Hence, the spectrometer is well suited to study kinetic processes of multiple infrared active compounds in reactive plasmas. A special data processing and analysis technique has been established to account for time jitter effects of the infrared emission of the QCLs. The performance of the TRIPLE Q system has been validated in pulsed direct current plasmas containing N2O/air and NO2/air. [ABSTRACT FROM AUTHOR]

Abstract: Reactive ion etch processes for modern interlevel dielectrics become more and more complex, especially for further scaling of interconnect dimensions. The materials will be damaged within such processes with the result of an increase in their dielectric constants. The capability of selected additives to minimize the low-k sidewall damage during reactive ion etching (RIE) of SiCOH materials in fluorocarbon plasmas was shown in different works in the past. Most of the investigated additive gases alter the fluorine to carbon ratio as well as the dissociation of the parent gas inside the etch plasma. The result is a changed etch rate, a modified polymerization behavior and other characteristics of the process induced SiCOH damage. Heavy inert ions like argon will be accelerated to the sample surface in the cathode dark space and enhance therewith the sputter yield on the SiCOH network . In this paper the additives Ar, O2, C4F8, H2, N2 and CO were added to a conventional CF4 etch plasma. We try to provoke different changes in the plasma conditions and therewith in the process results. Contact angle measurements, spectroscopic ellipsometry, Hg-probe analysis, FTIR measurements and SEM cross-sections were used to overview the additive induced modifications. To understand the influences of the additives gases more exactly, changes in the physical and chemical plasma behavior must be analyzed. Therefore quadrupole mass spectrometry (QMS) and quantum cascade laser absorption spectroscopy (QCLAS) were used. [Copyright &y& Elsevier]

A low pressure recombining Ar plasma to which mixtures of N2 and O2 were added has been studied to explore the relevance of surface related processes for the total chemistry. The abundances of the stable molecules N2, O2, NO, N2O and NO2 have been measured by means of a combination of infrared tunable diode laser absorption spectroscopy and mass spectrometry.A gas phase chemical kinetics model was developed in CHEMKIN to investigate the contribution of homogeneous interactions to the conversion of the feedstock gases N2 and O2. At a partial pressure of N2 plus O2 less than 8 Pa, significant discrepancies between measured and calculated concentrations of N2O and NO2 were observed, indicating that heterogeneous processes are dominating the chemistry in this pressure range. At a partial pressure of N2 plus O2 higher than 40 Pa and a relatively high fraction of admixed O2 we observed a fair agreement between measured and calculated concentrations of NO molecules, indicating that homogeneous processes (notably N atom induced) are more dominant than heterogeneous processes. [ABSTRACT FROM AUTHOR]

Abstract: A hot filament plant for chemical vapor deposition of crystalline diamond featuring new operating stages has been built. It allows (i) a separate methane feed locally at substrate position and (ii) supplying a forced gas flow towards the substrate. To understand the effect of these two features on diamond growth, the results of systematic diamond growth experiments are discussed. To reveal the effects of these features on the gas phase, infrared tunable diode laser absorption spectroscopy (IR-TDLAS) was employed. Using a forced gas flow showed a remarkable increase in the diamond growth rate of a factor >6 compared to standard coating setups. By lowering the methane content in the forced flow diamond quality factors >95% were achieved. IR-TDLAS showed an increase of all measured carbon-containing species CH4, C2H2, CH3 and CO when applying the forced flow. The mass transport dominated by diffusion in the standard setup shifts to a convective gas transport in the forced flow setup. The induced laminar flow causes a more effective transport of the growth species to the substrate and leads to higher growth rates. Application of feeding methane locally at substrate position leads to exceptionally high growth rates (0.68μm/h) at correspondingly high diamond quality (91%). For this, the methane content has to be lowered, though, which at the same time leads to a more homogenous deposition lateral on the surface. From the IR-TDLAS gas phase measurements, a more effective precursor dissociation, a higher CH3 density and a rise in the CH3⧸C2H2 ratio above the substrate surface can be derived. [Copyright &y& Elsevier]

Abstract: In hot-filament CVD the gas-phase composition is a vital parameter for diamond coating results. Concentrations of carbon-containing species have significant influence on growth rate, quality and morphology of deposited diamond. To learn more about the correlations between process parameters and gas species concentrations we applied the highly sensitive infrared tunable diode laser absorption spectroscopy (IR-TDLAS) technique. With a sophisticated compact IR-TDLAS unit, relative and absolute concentrations of CH4, C2H2 and CO were simultaneously measured. Also, the absolute concentration of the methyl radical was determined in dependence on process parameters. Concentrations of CO2, C2H6 and HCN were investigated but found to be lower than the detection limit. The influence of the typical diamond CVD-process parameters on various species concentrations is discussed. The applicability of IR-TDLAS for hot-filament process monitoring is evaluated. In context with diamond growth results, information for CVD process refinement was deducted from the IR-TDLAS measurements. [Copyright &y& Elsevier]

Rotationally resolved spectra of the fundamental band of the CN free radical in four isotopic forms have been measured using tunable diode laser absorption spectroscopy. The source of the radical was a microwave discharge in a mixture of isotopically selected methane and nitrogen diluted with argon. The lines were measured to an accuracy of 5×10-4 cm-1 and fitted to the formula for the vibration rotation spectrum of a diatomic molecule, including quartic distortion constants. The band origins of each of the isotopomers from the five parameter fits were found to be 12C14N: 2042.42115(38) cm-1, 13C14N: 2000.08479(23) cm-1, 12C15N: 2011.25594(25) cm-1, 13C15N: 1968.22093(33) cm-1 with one standard deviation from the fit given in parenthesis. Some of the lines showed a resolved splitting due to the spin rotation interaction. This was averaged for fitting purposes. The average equilibrium internuclear distance derived from the v=0 and 1 rotational constants of the four isotopomers is 1.171800(6) Å which is in good agreement with the value determined from microwave spectroscopy. [Copyright &y& Elsevier]

A compact and transportable two laser beam infrared (TOBI) system based on infrared absorption spectroscopy has been developed for time-resolved plasma diagnostics. The TOBI system contains two independent tunable diode lasers which can be directed through a plasma or into a multipass cell for exhaust gas detection. Rapid scan software with real-time line shape fitting provides a time resolution up to 10 μs to study chemical kinetic processes of infrared active compounds in plasmas. The capabilities of the TOBI system have been demonstrated in plasmas of pulsed H[sub 2]–N[sub 2] surface wave and in pulsed air–CH[sub 4] dc discharges. © 2003 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Using a three-stage dielectric packed-bed plasma reactor at atmospheric pressure, the destruction of ethylene, a typical volatile organic compound, and the generation of major by-products have been studied by means of Fourier Transform Infrared Spectroscopy. A test gas mixture air at a gas flow of 1 slm containing 0.12% humidity with 0.1% ethylene has been used. In addition to the fragmentation of the precursor gas, the evolution of the concentration of ten stable reaction products, CO, CO2, O3, NO2, N2O, HCN, H2O, HNO3, CH2O, and CH2O2 has been monitored. The concentrations of the by-products range between 5 ppm, in the case of NO2, and 1200 ppm, for H2O. By the application of three sequentially working discharge cells at a frequency of f = 4 kHz and voltage values between 9 and 12 kV, a nearly complete decomposition of C2H4 could be achieved. Furthermore, the influence of the specific energy deposition (SED) on the destruction process has been studied and the maximum value of SED was about 900 J l-1. The value of the characteristic energy β, characterizing the energy efficiency of the ethylene destruction in the reactor, was found to be 330 J l-1. It was proven that the application of three reactor stages suppresses essentially the production of harmful by-products as formaldehyde, formic acid, and NO2 compared to the use of only one or two stages. Based on the multi-component detection, the carbon balance of the plasma chemical conversion of ethylene has been analyzed. The dependence of the fragmentation efficiencies of ethylene (RF(C2H4) = 5.5 × 1019 molecules J-1) and conversion efficiencies to the produced molecular species (RC = (0.1-3) × 1016 molecules J-1) on the discharge conditions could be estimated in the multistage plasma reactor. [ABSTRACT FROM AUTHOR]

The effect of combining plasma and photocatalyst for Volatile Organic Compounds (VOC) removal was investigated in a pulsed low-pressure dc discharge. The photocatalyst was TiO2 while the VOC was acetylene (1000 ppm) diluted in dry air. The temporal evolution of C2H2 concentration was measured by Tunable Diode Laser Absorption Spectroscopy (TDLAS) in the mid-infrared region during the plasma pulse (one second). The contribution of external ultraviolet radiation and plasma exposure were quantified, both with and without a photocatalyst. The synergetic effect was clearly demonstrated. [ABSTRACT FROM AUTHOR]