Glow discharge

much about the atomic interactions in the gas, so glow

discharge is used in plasma physics and analytical chemistry. It is also used in the surface treatment technique
called sputtering.

1 Basic operating mechanism

A glow discharge tube featuring its most important characteristics: (a) An anode at one end and cathode at the other end (b)
Aston Dark Space(c) Cathode glow (d) Cathode dark space (also
called Crookes dark space, or Hittorf dark space) (e) Negative
glow (f) Faraday space (g) Positive column (h) Anode glow (i)
Anode dark space.

This system was rst made by William Crookes. The

simplest type of glow discharge is a direct-current glow
discharge. In its simplest form, it consists of two electrodes in a cell held at low pressure (0.110 torr; about
1/10000th to 1/100th of atmospheric pressure). The cell
is typically lled with neon, but other gases can also be
used. An electric potential of several hundred volts is
applied between the two electrodes. A small fraction of
the population of atoms within the cell is initially ionized
through random processes (thermal collisions between
atoms or with gamma rays, for example). The ions (which
are positively charged) are driven towards the cathode by
Neon lamp, 1/2 inch, showing glow discharge surrounding cath- the electric potential, and the electrons are driven towards
the anode by the same potential. The initial population
ode.
of ions and electrons collides with other atoms, ionizing
A glow discharge is a plasma formed by the passage of them. As long as the potential is maintained, a population
electric current through a low-pressure gas. It is created of ions and electrons remains.
by applying a voltage between two metal electrodes in a Some of the ions kinetic energy is transferred to the
glass tube containing gas. When the voltage exceeds a cathode. This happens partially through the ions strikcertain value called the striking voltage, the gas in the ing the cathode directly. The primary mechanism, howtube ionizes, becoming a plasma, and begins conduct- ever, is less direct. Ions strike the more numerous neuing electricity, causing it to glow with a colored light. tral gas atoms, transferring a portion of their energy
The color depends on the gas used. Glow discharge is to them. These neutral atoms then strike the cathode.
widely used as a source of light in devices such as neon Whichever species (ions or atoms) strike the cathode, collights, uorescent lamps, and plasma-screen televisions. lisions within the cathode redistribute this energy until a
Analyzing the light produced by spectroscopy can reveal portion of the cathode is ejected, typically in the form of
1

2 USE IN ANALYTICAL CHEMISTRY

positive column will be compressed while the negative
glow will remain the same size, and, with small enough
gaps, the positive column will disappear altogether. In
an analytical glow discharge, the discharge is primarily a
negative glow with dark region above and below it.

K
10 0

Current (A)

Arc

J
Abnormal
Glow
H
G
Normal F
Glow

105

I
Glow
Discharge

F'

"breakdown"

E'

1010

C
B

A
1015

B'

A'
0

Dark
Discharge

200

400

600

800

1000

Voltage (V)
Current-voltage curve (characteristic curve) of a discharge in
neon gas at a pressure of 1 torr, showing the dierent regions.
The vertical (current) scale is logarithmic.

free atoms. This process is known as sputtering. Once

free of the cathode, atoms move into the bulk of the glow
discharge through drift and due to the energy they gained
from sputtering. The atoms can then be excited by collisions with ions, electrons, or other atoms that have been
previously excited by collisions. Once excited, atoms will
lose their energy fairly quickly. Of the various ways that
this energy can be lost, the most important is radiatively,
meaning that a photon is released to carry the energy
away. In optical atomic spectroscopy, the wavelength of
this photon can be used to determine the identity of the
atom (that is, which chemical element it is) and the number of photons is directly proportional to the concentration of that element in the sample. Some collisions (those
of high enough energy) will cause ionization. In atomic
mass spectrometry, these ions are detected. Their mass
identies the type of atoms and their quantity reveals the
amount of that element in the sample.
The gure above shows the main regions that may be
present in a glow discharge. Regions described as glows
emit signicant light; regions labeled as dark spaces
do not. As the discharge becomes more extended (i.e.,
stretched horizontally in the geometry of the gure), the
positive column may become striated. That is, alternating dark and bright regions may form. Compressing the
discharge horizontally will result in fewer regions. The

Below the ionization voltage or breakdown voltage there

is no glow, but as the voltage increases to the ionization
point the Townsend discharge happens just as glow discharge becomes visible; this is the start of the normal
glow range. As the voltage is increased above the normal glow range, abnormal glow begins. If the voltage is
increased to the point the cathode glow covers the entire
cathode arc discharge begins.[1]

2 Use in analytical chemistry

Glow discharges can be used to analyze the elemental,
and sometimes molecular, composition of solids, liquids,
and gases, but elemental analysis of solids is the most
common. In this arrangement, the sample is used as the
cathode. As mentioned earlier, gas ions and atoms striking the sample surface knock atoms o of it, a process
known as sputtering. The sputtered atoms, now in the
gas phase, can be detected by atomic absorption, but this
is a comparatively rare strategy. Instead, atomic emission and mass spectrometry are usually used. Collisions
between the gas-phase sample atoms and the plasma gas
pass energy to the sample atoms. This energy can excite the atoms, after which they can lose their energy
through atomic emission. By observing the wavelength of
the emitted light, the atoms identity can be determined.
By observing the intensity of the emission, the concentration of atoms of that type can be determined. Energy gained through collisions can also ionize the sample
atoms. The ions can then be detected by mass spectrometry. In this case, it is the mass of the ions that identify the
element and the number of ions that reect the concentration. This method is referred to as glow discharge mass
spectrometry (GDMS) and it has detection limits down
to the sub-ppb range for most elements that are nearly
matrix-independent.
Both bulk and depth analysis of solids may be performed
with glow discharge. Bulk analysis assumes that the sample is fairly homogeneous and averages the emission or
mass spectrometric signal over time. Depth analysis relies on tracking the signal in time, therefore, is the same
as tracking the elemental composition in depth. Depth
analysis requires greater control over operational parameters. For example, conditions (current, potential, pressure) need to be adjusted so that the crater produced by
sputtering is at bottom (that is, so that the depth analyzed
over the crater area is uniform). In bulk measurement, a
rough or rounded crater bottom would not adversely impact analysis. Under the best conditions, depth resolution
in the single nanometer range has been achieved (in fact,
within-molecule resolution has been demonstrated).

3
The chemistry of ions and neutrals in vacuum is called shortest route between two points. The Nature news artigas phase ion chemistry and is part of the analytical study cle describes the system as follows:
that includes glow discharge.
To make the one-inch London chip, the team
etched a plan of the city centre on a glass
slide. Fitting a at lid over the top turned
3 Powering modes
the streets into hollow, connected tubes. They
lled these with helium gas, and inserted elecIn analytical chemistry, glow discharges are most often
trodes at key tourist hubs. When a voltage is
operated in direct-current mode. For this mode, the cathapplied between two points, electricity natuode (which is the sample in solids analysis) must be conrally runs through the streets along the shortest
ductive. The potential, pressure, and current are interreroute from A to B - and the gas glows like a tiny
lated. Only two can be directly controlled at once, while
neon strip light.
the third must be allowed to vary. The pressure is most
typically held constant, but other schemes may be used.
The approach itself provides a novel visible analog comThe pressure and current may be held constant, while poputing approach for solving a wide class of maze searchtential is allowed to vary. The pressure and voltage may
ing problems based on the properties of lighting up of a
be held constant while the current is allowed to vary. The
glow discharge in a microuidic chip.
power (product of voltage and current) may be held constant while the pressure is allowed to vary.
Glow discharges may also be operated in radio-frequency.
The use of this frequency will establish a negative DCbias voltage on the sample surface. The DC-bias is the
result of an alternating current waveform that is centered
about negative potential; as such it more or less represent the average potential residing on the sample surface.
Radio-frequency has ability to appear to ow through insulators (non-conductive materials).
Both radio-frequency and direct-current glow discharges
can be operated in pulsed mode, where the potential is
turned on and o. This allows higher instantaneous powers to be applied without excessively heating the cathode. These higher instantaneous powers produce higher
instantaneous signals, aiding detection. Combining timeresolved detection with pulsed powering results in additional benets. In atomic emission, analyte atoms emit
during dierent portions of the pulse than background
atoms, allowing the two to be discriminated. Analogously, in mass spectrometry, sample and background
ions are created at dierent times.

Types

There are various types of glow discharge examples include: high pressure glow discharge, hollow cathode discharge, spray discharge.

Application to analog computing

An interesting application for using glow discharge was

described in a 2002 scientic paper by Ryes, Ghanem et
al.[2] According to a Nature news article describing the
work,[3] researchers at Imperial College London demonstrated how they built a mini-map that glows along the

6 See also
Electric arc discharge
Vacuum arc
X-ray tube
Fluorescent lamp, neon lamp, and plasma lamp
List of plasma (physics) articles

7 References
[1] Principles of Electronics By V.K. Mehta ISBN 81-2192450-2
[2] Reyes, D. R.; Ghanem, M. M.; Whitesides, G. M.; Manz,
A. (2002). Glow discharge in microuidic chips for visible analog computing. Lab on a Chip (ACS) 2 (2): 113
6. doi:10.1039/B200589A. PMID 15100843.
[3] Mini-map
gives
tourists
neon
route
http://www.nature.com/news/2002/020527/full/
news020520-12.html

signs:

8 Further reading
S. Flgge, ed.
(1956).
Handbuch der
Physik/Encyclopedia of Physics band/volume XXI
- Electron-emission Gas discharges I. SpringerVerlag. First chapter of the article Secondary
eects by P.F. Little.
R. Kenneth Marcus (Ed.) (1993). Glow Discharge
Spectroscopies. Kluwer Academic Publishers (Modern Analytical Chemistry). ISBN 0-306-44396-1.

9 TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES

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