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Application of quantum cascade lasers and infrared-fibres for the monitoring and control of industrial plasma processes
Abstract
Quantum cascade lasers (QCL) offer attractive options for the application of mid-infrared absorption spectroscopy for industrial process monitoring and control. In particular the in-situ measurement of reactive plasma compounds can give new insight into the reaction kinetics of industrial plasma processes. For these purposes the compact quantum cascade laser measurement and control system (Q-MACS) has been combined with an infrared-fibre to allow a flexible and completely dust-sealed incoupling of the infrared radiation into the reactor chamber of an industrial plasma surface modification system. The system has been completed with a fast and compact detector and a data acquisition system to monitor concentrations of species of interest in the plasma process online. First tests proofed the potential of this approach.
... All inter pulse spectra were normalized to a previously acquired baseline (dotted line). (c) Time resolved BCl 3 mixing ratios measured in a H 2 /Ar/BCl 3 MW discharge (2 mbar) using the advanced fit procedure for complex spectra depicted in (b) (adapted and enlarged from [63]). ...
The recent availability of thermoelectrically cooled pulsed and continuous wave quantum and inter-band cascade lasers in the mid-infrared spectral region has led to significant improvements and new developments in chemical sensing techniques using in-situ laser absorption spectroscopy for plasma diagnostic purposes. The aim of this article is therefore two-fold: (i) to summarize the challenges which arise in the application of quantum cascade lasers in such environments, and, (ii) to provide an overview of recent spectroscopic results (encompassing cavity enhanced methods) obtained in different kinds of plasma used in both research and industry.
Owing to recent technological advances in mid‐infrared (MIR) laser sources, cascade laser spectroscopy (CLS) has evolved to a promising modern technique for high selective and sensitive quantification of trace gases in many sensing scenarios. High output power, narrow linewidths, single‐mode operation, low power consumption besides compactness are just some of the outstanding features of cascade lasers. Since their discovery, quantum cascade lasers (QCL) and interband cascade lasers (ICL) have made rapid progress and has established themselves as the most important MIR laser sources. In this article, we provide a brief overview of state‐of‐the‐art spectroscopic techniques in cascade laser spectroscopy associated with their fundamental principles, including direct absorption spectroscopy (DAS), wavelength modulation spectroscopy (WMS), photoacoustic spectroscopy (PAS), and optical cavity enhanced spectroscopy (OCES). A number of selected spectroscopy applications of QCL‐ and ICL‐based optical systems for industrial process control, medical applications, and standoff detection for security are reviewed.
In situ measurements are reported giving insight into the plasma chemical conversion of the precursor BCl3 in industrial applications of boriding plasmas. For the online monitoring of its ground state concentration, quantum cascade laser absorption spectroscopy (QCLAS) in the mid-infrared spectral range was applied in a plasma assisted chemical vapor deposition (PACVD) reactor. A compact quantum cascade laser measurement and control system (Q-MACS) was developed to allow a flexible and completely dust-sealed optical coupling to the reactor chamber of an industrial plasma surface modification system. The process under the study was a pulsed DC plasma with periodically injected BCl3 at 200 Pa. A synchronization of the Q-MACS with the process control unit enabled an insight into individual process cycles with a sensitivity of 10⁻⁶ cm⁻¹Hz-1/2. Different fragmentation rates of the precursor were found during an individual process cycle. The detected BCl3 concentrations were in the order of 10¹⁴ moleculescm⁻³. The reported results of in situ monitoring with QCLAS demonstrate the potential for effective optimization procedures in industrial PACVD processes.
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.
Development of infrared (IR) fibers and hollow waveguides (HWGs) was in good progress to meet growing market demands for laser power delivery, flexible IR-imaging and remote process-spectroscopy in spectral range from 1 to 18 μm. Parameters of IR-glass fibers, polycrystalline IR-fibers (PIR-fibers) from silver halides and HWGs are compared to enable optimal choice for the production of IR-cables, spectroscopy probes and multispectral bundles (Fig. 1).
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.
This paper reviews recent progress in the development of time-resolved diagnostics to probe high-density pulsed plasma sources. We focus on time-resolved measurements of radicals' densities in the afterglow of pulsed discharges to provide useful information on production and loss mechanisms of free radicals. We show that broad-band absorption spectroscopy in the ultraviolet and vacuum ultraviolet spectral domain and threshold ionization modulated beam mass spectrometry are powerful techniques for the determination of the time variation of the radicals' densities in pulsed plasmas. The combination of these complementary techniques allows detection of most of the reactive species present in industrial etching plasmas, giving insights into the physico-chemistry reactions involving these species. As an example, we discuss briefly the radicals' kinetics in the afterglow of a SiCl4/Cl2/Ar discharge.
In situ measurements are reported giving insight into the plasma chemical conversion of the precursor BCl3 in industrial applications of boriding plasmas. For the online monitoring of its ground state concentration, quantum cascade laser absorption spectroscopy (QCLAS) in the mid-infrared spectral range was applied in a plasma assisted chemical vapor deposition (PACVD) reactor. A compact quantum cascade laser measurement and control system (Q-MACS) was developed to allow a flexible and completely dust-sealed optical coupling to the reactor chamber of an industrial plasma surface modification system. The process under the study was a pulsed DC plasma with periodically injected BCl3 at 200 Pa. A synchronization of the Q-MACS with the process control unit enabled an insight into individual process cycles with a sensitivity of 10-6 cm-1\cdotHz-1/2. Different fragmentation rates of the precursor were found during an individual process cycle. The detected BCl3 concentrations were in the order of 1014 molecules\cdotcm-3. The reported results of in situ monitoring with QCLAS demonstrate the potential for effective optimization procedures in industrial PACVD processes.
Broad band UV-visible absorption spectroscopy is widely used to measure the concentration of radicals in reactive plasmas. We extended the applicability of this technique to the VUV (115 nm to 200 nm), the spectral range in which the electronic transitions from the ground state to the Rydberg or pre-dissociated states of many closed-shell molecules are located. This gives access to the absolute densities of species which do not, or weakly absorb in the UV-visible range. The technique is demonstrated by measuring the densities of HBr and Br2 molecules in HBr high-density ICP plasmas.
Boron trichloride (BCl3) is used as a source gas in various industrial plasma applications. The online monitoring of its ground state concentration in the plasma process reactor is vital for improved insight into the plasma chemistry and to increase productivity, reliability and reproducibility of the process. Infrared absorption spectroscopy was applied for in situ measurements of absolute densities of BCl3 and HCl in planar microwave plasma sources as well as in an industrial pulsed dc discharge reactor. In this paper procedures for the determination of HITRAN format line strength data files for BCl3 are described together with results of concentration measurements. The results show the influence of the discharge parameters on the dissociation of BCl3 and its conversion to HCl. Observations using tuneable diode lasers are compared with measurements using quantum cascade lasers and the applicability of this diagnostic technique for industrial plasma process monitoring is shown.
The recent development of quantum cascade lasers (QCLs) offers an attractive new option for the monitoring and control of industrial plasma processes and for trace-gas analysis as well as for highly time-resolved studies on the kinetics of plasma processes. The contribution reviews selected examples of the application of QCLs for infrared absorption studies in basic research and for plasma monitoring and control in industry.
The kinetics of stable species has been studied in situ in pulsed CF4/H2 radio frequency discharges by means of time resolved quantum cascade laser absorption spectroscopy. The absorption spectra were usually recorded with a time resolution of 5 ms and required a multi-species analysis, because of interfering complex absorption features of CF4 and C3F8. For this reason, measurements were carried out at two different spectral positions. High resolution spectroscopic data were established by calibrating effective absorption cross sections and their relative temperature dependences for the relevant low pressure conditions (10 Pa). During the discharge a decrease in the CF4 density by ~12% was observed. The off-phase was characterized mainly by the gas exchange. The C3F8 density in the off-phase was found to be of the order of the detection limit (3 × 1013 cm−3). Spectra acquired during the plasma-on phase showed a rapid temperature-induced increase in the absorption signal and, additionally, suggested the influence of a short-lived broadband absorbing species. The reasonable assumption of the presence of CF4 hotbands has not yet enabled a further quantification.
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 CH4 absorption features around 1347cm−1 (7.42μm) 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.
A compact and transportable infrared multicomponent acquisition (IRMA) system based on infrared absorption spectroscopy has been developed for plasma diagnostics and control. The IRMA system contains four independent tunable diode lasers which can be temporally multiplexed and directed into plasma reactors or into a multipass cell for exhaust gas detection. Rapid scan software with real-time line shape analysis provides simultaneous measurements of the absolute concentrations of several molecular species. © 2000 American Institute of Physics.
This paper describes the status of the 2004 edition of the HITRAN molecular spectroscopic database. The HITRAN compilation consists of several components that serve as input for radiative transfer calculation codes: individual line parameters for the microwave through visible spectra of molecules in the gas phase; absorption cross-sections for molecules having dense spectral features, i.e., spectra in which the individual lines are unresolvable; individual line parameters and absorption cross-sections for bands in the ultra-violet; refractive indices of aerosols; tables and files of general properties associated with the database; and database management software. The line-by-line portion of the database contains spectroscopic parameters for 39 molecules including many of their isotopologues.The format of the section of the database on individual line parameters of HITRAN has undergone the most extensive enhancement in almost two decades. It now lists the Einstein A-coefficients, statistical weights of the upper and lower levels of the transitions, a better system for the representation of quantum identifications, and enhanced referencing and uncertainty codes. In addition, there is a provision for making corrections to the broadening of line transitions due to line mixing.
Tunable infrared diode laser absorption spectroscopy has been used to detect the methyl radical and ten stable molecules in H2-Ar-O2microwave plasmas containing up to 7.2% of methane or methanol, under both flowing and static conditions. The degree of dissociation of the hydrocarbons varied between 30 and 90% and the methyl radical concentration was found to be in the range 1010–1012molecules cm-3. The methyl radical concentration and the concentrations of the stable C-2 hydrocarbons C2H2, C2H4, and C2H6, produced in the plasma decayed exponentially when increasing amounts of O2were added at fixed methane or methanol partial pressures. In addition to detecting the hydrocarbon species, the major products CO, CO2, and H2O were also monitored. For the first time, formaldehyde, formic acid, and methane were detected in methanol microwave plasmas, formaldehyde was detected in methane microwave plasmas. Chemical modeling with 57 reactions was used to successfully predict the concentrations in methane plasmas in the absence of oxygen and the trends for the major chemical product species as oxygen was added.
Tunable infrared diode laser absorption spectroscopy has been used to detect the methyl radical and nine stable molecules, CH4, CH3OH, C2H2, C2H4, C2H6, NH3, HCN, CH2O and C2N2, in H2–Ar–N2 microwave plasmas containing up to 7% of methane or methanol, under both flowing and static conditions. The degree of dissociation of the hydrocarbon precursor molecules varied between 20% and 97%. The methyl radical concentration was found to be in the range 1012–1013 molecules cm−3. By analysing the temporal development of the molecular concentrations under static conditions it was found that HCN and NH3 are the final products of plasma chemical conversion. The fragmentation rates of methane and methanol (RF(CH4) = (2–7) × 1015 molecules J−1, RF(CH3OH) = (6–9) × 1015 molecules J−1) and the respective conversion rates to methane, hydrogen cyanide and ammonia (RCmax(CH4) = 1.2 × 1015 molecules J−1, RCmax(HCN) = 1.3 × 1015 molecules J−1, RCmax(NH3) = 1 × 1014 molecules J−1) have been determined for different hydrogen to nitrogen concentration ratios. An extensive model of the chemical reactions involved in the H2–N2–Ar–CH4 plasma has been developed. Model calculations were performed by including 22 species, 145 chemical reactions and appropriate electron impact dissociation rate coefficients. The results of the model calculations showed satisfactory agreement between calculated and measured concentrations. The most likely main chemical pathways involved in these plasmas are discussed and an appropriate reaction scheme is proposed.
In etch plasmas used for semiconductor processing, concentrations of the precursor gas NF3 and of the etch product SiF4 are measured online and in situ using a new diagnostic arrangement, the Q-MACS Etch system, which is based on quantum cascade laser absorption spectroscopy (QCLAS). In addition, the etch rates of SiO2 layers and of the silicon wafer are monitored including plasma-etching endpoint detection. For this purpose the Q-MACS Etch system is working as an interferometer arrangement. The experiments are performed in an industrial, dual-frequency, capacitively coupled, magnetically enhanced, reactive ion etcher (MERIE), which is a plasma reactor developed for dynamic random access memory (DRAM) technologies. In the spectral range 1028 ± 0.3 cm–1, the absorption cross-sections of SiF4 and NF3 are determined to be σ = (7.7 ± 0.7) × 10–18 cm2 molecule–1 and σ = (8.7 ± 0.8) × 10–20 cm2 molecule–1, respectively.
Non-cryogenic, laser-absorption spectroscopy in the mid-infrared has wide applications for practical detection of trace gases
in the atmosphere. We report measurements of nitric oxide in air with a detection limit less than 1nmole/mole (<1ppbv) using
a thermoelectrically cooled quantum cascade laser operated in pulsed mode at 5.26μm and coupled to a 210-m path length multiple-pass
absorption cell at reduced pressure (50Torr). The sensitivity of the system is enhanced by operating under pulsing conditions
which reduce the laser line width to 0.010cm-1 (300MHz) HWHM, and by normalizing pulse-to-pulse intensity variations with temporal gating on a single HgCdTe detector.
The system is demonstrated by detecting nitric oxide in outside air and comparing results to a conventional tunable diode
laser spectrometer sampling from a common inlet. A detection precision of 0.12ppb Hz-1/2 is achieved with a liquid-nitrogen-cooled detector. This detection precision corresponds to an absorbance precision of 1×10-5Hz-1/2 or an absorbance precision per unit path length of 5×10-10cm-1 Hz-1/2. A precision of 0.3ppb Hz-1/2 is obtained using a thermoelectrically cooled detector, which allows continuous unattended operation over extended time periods
with a totally cryogen-free instrument.
A technique has been developed for the determination of molecular parameters, including infrared absorption line positions, strengths, and nitrogen-broadened half-widths for 1,3-butadiene (C(4)H(6)) and propylene (C(3)H(6)). The parameters for these two molecules are required for quantitation using Tunable Diode Laser Absorption Spectroscopy (TDLAS). These molecules have populations of highly overlapping infrared absorption lines in their room temperature spectra. The technique reported here provides a procedure for estimating the molecular parameters for these overlapping absorption lines from quantitative reference spectra taken with the TDLAS instrument at different pressures and concentrations. The system was developed for the quantitation of gaseous constituents in a single puff of cigarette smoke and this paper will describe the procedure and some of the factors that influence the accuracy of quantitation for 1,3-butadiene, including the approach taken to minimize the adverse effects of the absorption due to propylene in the same spectral region.
Acrolein (C(3)H(4)O) molecular line parameters, including infrared (IR) absorption positions, strengths, and nitrogen broadened half-widths, must be determined since they are not included in the high resolution transmission (HITRAN) molecular absorption database of spectral lines. These parameters are required for developing a quantitative analytical method for measuring acrolein in a single puff of cigarette smoke using tunable diode laser absorption spectroscopy (TDLAS). The task is complex since acrolein has many highly overlapping infrared absorption lines in the room temperature spectrum and the cigarette smoke matrix contains thousands of compounds. This work describes the procedure for estimating the molecular line parameters for these overlapping absorption lines in the wavenumber range (958.7-958.9 cm(-1)) using quantitative reference spectra taken with the infrared lead-salt TDLAS instrument at different pressures and concentrations. The nitrogen broadened half-width for acrolein is 0.0937 cm(-1)atm(-1) and to our knowledge, is the first time it has been reported in the literature.
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