ReviewPulsed glow discharges for analytical applications
Introduction
Glow discharge (GD), coupled to optical emission (GDOES) or mass spectrometry (GDMS), is now an established technique for direct analysis of solid samples [1], [2]. In particular, when a Grimm type source [3] is used or a modified design based on Grimm's geometry [4], [5], [6], [7] glow discharge analytical instruments are appreciated for their superb depth resolution [8], [9]. The relative ease of use and straight forwardness of data interpretation[10] are also appreciated by the analysts. Commercial GD spectrometers are employing DC sources for conductive materials and RF sources for both conductive and non-conductive samples [11] and cover a large range of applications [12]. GDOES instruments are used for bulk analysis of homogeneous samples as well as for surface, depth profile and interface analysis. GDMS instruments employing high resolution sector field spectrometers offer detection limits in the low ppb range [13] and beyond but; due to the sequential ion detection, the field of application of these instruments is restricted to bulk analysis and possibly depth profile analysis of rather thick layers in the micrometer range [14], [15].
Pulsing the glow discharge offers a number of advantages [16]. One is to provide an additional way of controlling the plasma by choosing the pulse parameters, such as pulse length and period, in order to select optimal discharge conditions (Fig. 1). Another interesting property is that the instantaneous power, responsible for the sputtering, excitation and ionisation yields can be chosen nearly independent from the average power responsible for thermal stress on the sample, by varying the duty cycle of the applied pulses. Finally within a single pulse different discharge processes take place at different times allowing selective measurements if a time resolved acquisition is available [17].
The first optical glow discharge spectrometers based on the Grimm source, were commercialized by RSV in the 1980s. They used a pulsed (400 Hz) dc power supply. In these instruments, the average discharge power was adapted to the analytical needs by varying the pulse duty cycle at fixed instantaneous excitation voltage. Later, when surface and interface analysis became the most important field of applications of GDOES spectrometry, continuous sources were used. Today many high-end instruments are again equipped with optional pulsed sources, but to our knowledge, none of the commercially available instruments exploits the intrinsic advantages of modulated excitation and time resolved data acquisition (except for a locally available system provided by Horiba in Japan [18]).
By comparison, in spark-OES and Atomic Absorption Spectroscopy [19], considerable improvements of the analytical performance have been achieved using time resolved detection and data analysis techniques.
Section snippets
Physical aspects
This review deals with the analytical applications of pulsed glow discharges. Understanding the analytical benefit of pulsing a glow discharge requires some insight into the underlying physical processes. First we will deal with the time characteristics of the main processes occurring in a glow discharge and give some information on the dynamics of the sheaths. We will then focus on the ignition phase and the afterglow.
Analytical applications
Glow discharges are used as a versatile tool in analytical sciences. They are applied to the direct analysis of homogeneous solids, generally conducting materials. Using radio frequency excitation of the discharge, non-conducting materials can also be analyzed, though the lack of adequate certified reference materials often does not allow a precise quantification for non-conductors. For this “bulk” application the most important factors are the limits of detection, the time and ease of analysis
Conclusion
In this review we have tried to demonstrate that glow discharges may well be exciting plasmas [141], but pulsed glow discharges are even more exciting. The temporal sequence of ignition, plateau and afterglow gives access to more information than just stable operation. During short pulses, transient conditions can be obtained, which are not accessible to continuous operation.
In the first part we have concentrated on the physical aspects of the pulsed operation of a glow discharge, giving some
Acknowledgement
The authors are member of the Technological Research Team ERT 2000, CUFR JFC Albi, FR and gratefully acknowledge financial support from the European Community through the FP6 contracts STREP-NMP no. 032202 (EMDPA) and MRTN-CT-2006-035459 (GLADNET). We would like to thank L. Pitchford (Laplace, Toulouse, Fr); A. Martin (Shiva Technologies, Tournefeuille, Fr), L. Thérèse (CURF JFC, Albi, Fr) and P. Chapon (Horiba Jobin Yvon, Lonjumeau, Fr) for stimulating discussions during the preparation phase
References (156)
Eine neue glimmentladungslampe für die optische emissionsspektralanalyse
Spectrochim. Acta Part B
(1968)- et al.
Depth profile and quantitative trace element analysis of diffusion aluminided type layers on Ni-base superalloys using high-resolution glow-discharge mass spectrometry
Surf. Coat. Technol.
(2001) Fundamentals of pulsed plasmas for materials processing
Surf. Coat. Technol.
(2004)- et al.
Design and characterisation of glow discharge devices as complementary sources for an ICP mass spectrometer
Spectrochimica. Acta Part B
(1991) - et al.
Electrical measurements at radio frequency glow discharges for spectroscopy
Spectrochim. Acta Part B
(2007) Townsend's ionization coefficients for neon, argon, krypton and xenon
Physica
(1940)- et al.
Electrical characteristics of a millisecond pulsed glow discharge
Spectrochim. Acta Part B
(2008) - et al.
Spectral, spatial and temporal characteristics of a millisecond pulsed glow discharge: metastable argon atom production
Spectrochim. Acta Part B
(2001) - et al.
Probing excitation and ionization processes in millisecond-pulsed glow discharges in argon through the addition of nitrogen
Spectrochim. Acta Part B
(2003) - et al.
Fundamental studies on a planar-cathode direct current glow discharge. Part II: numerical modeling and comparison with laser scattering experiments
Spectrochim. Acta Part B
(2004)
Fundamental studies on a planar-cathode direct current glow discharge. Part I: characterization via laser scattering techniques
Spectrochim. Acta Part B
Behavior of the sputtered copper atoms, ions and excited species in a radio-frequency and direct current glow discharge
Spectrochim. Acta Part B
Estimated mass loss due to evaporation for zinc cathodes in analytical glow discharges
Spectrochim. Acta Part B
Langmuir-probe measurements of a pulsed and steady-state rf glow-discharge source and of an rf planar-magnetron source
Spectrochim. Acta B
Spectral, spatial and temporal characterization of a millisecond pulsed glow discharge: copper analyte emission and ionization
Spectrochim. Acta Part B
Ion formation processes in the afterpeak time regime of pulsed glow-discharge plasmas
J. Am. Soc. Mass Spectrom.
Quasi cw laser at 585.3 nm of the Ne I line in Ne–H mixture in a simple co-axial alternative discharge
Opt. Commun.
Monte Carlo analysis of the electron thermalization process in the afterglow of a microsecond dc pulsed glow discharge
Spectrochim. Acta Part B
Comparison of calculated and measured optical emission intensities in a direct current argon–copper glow discharge
Spectrochim. Acta Part B
Description of the argon-excited levels in a radio-frequency and direct current glow discharge
Spectrochim. Acta Part B
Electronic perturbation investigations into excitation and ionization in the millisecond pulsed glow discharge plasma
Spectrochim. Acta Part B
Glow Discharge Optical Emission Spectrometry
Glow Discharge Optical Emission Spectrometry: A practical Guide
Characterization of a simple glow discharge coupled to a time of flight mass spectrometer for in-depth profile analysis
J. Anal. At. Spectrom.
Some characteristics of a new planar glow-discharge source with and without magnetic field
Spectrochim. Acta Part B
Grimm-type glow discharge ion source for operation with a high resolution inductively coupled plasma mass spectrometry instrument
J. Anal. At. Spectrom.
Influence of discharge parameters on the resultant sputtered crater shapes for a radio frequency glow discharge atomic emission source
Anal. Chem.
Rf-GDOES depth profiling analysis of a monolayer of thiourea adsorbed on copper
J. Anal. At. Spectrom.
Glow discharge as a tool for surface and interface analysis
Appl. Spectr. Rev.
The concept of constant emission yield in GDOES
Anal. Bioanal. Chem.
Radio frequency powered glow discharge atomization/ionization source for solids mass spectrometry
Anal. Chem.
Application of glow discharge optical emission spectrometry in the steel industry
J. Anal. At. Spectrom.
Inorganic mass spectrometry of solid samples
Fres. J. Anal. Chem.
Measurement of hydrogen and deuterium concentration ion gold electroplated layer by glow discharge mass spectrometry
Electrochem. Solid-State Lett.
Trends in glow discharge spectroscopy
J. Anal. At. Spectrom.
Temporal considerations with a microsecond pulsed glow discharge
J. Anal. At. Spectrom.
Depth profile analysis of ultra thin organinc films and fragile materials in RF-GD-OES
Pulsed and transient modes of sputtering in a glow discharge spectrometry atomization by cathodic for atomic absorption
Anal. Chem.
Theoretical elastic collision frequency between electrons and neutral atoms in a cesium plasma
Phys. Rev.
Effective collision frequency of electrons in noble gases
J. Phys. B: At. Mol. Phys.
Numerical model of rf glow discharges
Phys. Rev. A
In situ depth measurements for GD-OES
J. Anal. At. Spectrom.
Characterisation of a pulsed rf-glow discharge in view of its use in OES
J. Anal. At. Spectrom.
Temporal and spatially resolved laser-scattering plasma diagnostics for the characterization of a ms-pulsed glow discharge
J. Anal. At. Spectrom.
Determination of titanium temperature and density in a magnetron vapor sputtering device assisted by two microwave coaxial excitation systems
J. Vac. Sci. Technol. A: Vac. Surf. Films
Ionic and neutral densities measurements by pulsed absorption spectroscopy in amplified magnetron discharges
J. Appl. Phys.
The concept of plasma cleaning in glow discharge spectrometry
J. Anal. At. Spectrom.
Plasma sheath formation by radio-frequency fields
Phys. Fluids
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2018, Analytica Chimica ActaCitation Excerpt :Pulsed glow discharge (pulsed-GD) based spectral sources are traditionally employed in mass spectrometry or optical emission spectroscopy measurements for fast direct analysis of solid materials, featuring high sensitivity and high depth resolution analytical characteristics [1–3]. Pulsed-GD sources are known to generate a dynamic plasma with several time regimes (e.g. prepeak, plateau and afterglow) related to different dominant ionization/excitation processes (e.g. spark, electron impact, asymmetric charge transfer or Penning ionization) [4–6]. Coupling and synchronisation of pulsed-GD ion sources with a fast mass analyser, such as the TOFMS, enables probing and detection of the analyte ion signals along the GD pulse time profile.