Fresenius J Anal Chem (2001) 369 : 320–327
S P E C I A L I S S U E PA P E R
S. Michael Angel · Dimitra N. Stratis ·
Kristine L. Eland · Tianshu Lai · Mark A. Berg ·
David M. Gold
LIBS using dual- and ultra-short laser pulses
Received: 1 August 2000 / Revised: 2 November 2000 / Accepted: 8 November 2000
Abstract Pre-ablation dual-pulse LIBS enhancement
data for copper, brass and steel using ns laser excitation
are reported. Although large enhancements are observed
for all samples, the magnitude of the enhancement is ma-
trix dependent. Whereas all of the dual-pulse studies used
ns laser excitation we see interesting effects when using
ps and fs laser excitation for single-pulse LIBS. LIBS
spectra of copper using 1.3 ps and 140 fs laser pulses
show much lower background signals compared to ns
pulse excitation. Also, the atomic emission decays much
more rapidly with time. Because of relatively low back-
grounds when using ps and fs pulses, non-gated detection
of LIBS is shown to be very effective. The plasma dissi-
pates quickly enough using ps and fs laser pulses, that
high pulse rates, up to 1000 Hz, are effective for increas-
ing the LIBS signal, for a given measurement time. Fi-
nally, a simple near-collinear dual-pulse fiber-optic LIBS
probe is shown to be useful for enhanced LIBS measure-
ments.
Introduction
Laser-induced breakdown spectroscopy (LIBS) is a useful
method for determining the elemental composition of
solids. This method has been recently reviewed [1–3] and
a number of different applications [4–13] have been de-
scribed. In the LIBS technique, a pulsed laser, typically a
Q-switched Nd:YAG laser, is used to generate a plasma
on the surface of a solid sample. Elemental analysis of the
sample is accomplished by measuring the emission of
atomic and ionic species in the plasma. The ability to form
S. M. Angel () · D. N. Stratis · K. L. Eland · T. Lai ·
M. A. Berg
Department of Chemistry and Biochemistry,
The University of South Carolina, Columbia, SC 29208, USA
D. M. Gold
Medical Technology Program,
Lawrence Livermore National Laboratory, Livermore, CA 94550,
USA
© Springer-Verlag 2001
a plasma on unprepared samples makes LIBS a very at-
tractive analytical technique. In fact, the sample needs
only to be optically accessible and optical fibers are often
used [9–13]. In addition, laser-ablation sampling offers
the ability to perform a spatially resolved analysis which
is important for heterogeneous samples [14].
Although LIBS holds much promise as a remote analy-
sis technique, the method suffers from poor detection lim-
its and reproducibility compared to other forms of ele-
mental analysis [15]. The processes involved in laser-in-
duced plasma formation, such as sample heating, ablation,
atomization, ionization and excitation, are quite complex
and difficult to reproduce. To address these problems,
some research groups are investigating the use of dual-
laser pulses for LIBS, where the laser pulses are separated
by a short delay time. In some cases, it has been shown
that the use of dual-laser pulses, or dual-pulse LIBS, can
lead to lower detection limits [16, 17], enhanced emission
signals [16–23], and improved internal standardization
[24].
Recently, we demonstrated a new dual-pulse LIBS
method that produces both enhanced emission signals and
material ablation through the use of a pre-ablation laser
spark [18]. Signal enhancements as high as 40-fold were
achieved using this pre-ablation spark dual-pulse LIBS
method. In this technique, the first laser pulse is brought
in parallel to the sample and focused above it to form an
air plasma. Although the plasma generated by the pre-ab-
lation spark heats the sample, it is sufficiently far from the
surface that sample ablation and emission are not ob-
served. LIBS emission is observed in the plasma that is
created by the second laser pulse, which is focused on the
sample. In all cases where enhanced LIBS signals were
seen, enhanced sample ablation also occurred [18]. Our
previous studies focused on pure metal and glass samples.
In this paper, we describe additional dual-pulse LIBS re-
sults on copper, brass and steel samples.
Lack of precision in LIBS is largely a result of poor re-
producibility in sample ablation. Recent laser ablation
work using short laser pulses, less than 20 ps, has shown
that such pulses reduce material deposition around the ab-

lation area and dramatically increase the reproducibility
of material ablation. Reproducibility is improved because
of reduced thermal damage and lower threshold fluences
of ablation of the material [25]. These effects are largely
attributed to the direct transition of material to the vapor
or plasma phase without melting. High precision ablation
using sub-picosecond laser pulses has been demonstrated
for metals, ceramics and polymers such as PTFE [25–30].
The use of ps and sub-ps laser pulses for laser-induced
plasma formation has been described, however, it is usu-
ally in the context of X-ray production [31–33], laser fu-
sion [34] or damage to optical components in high-power
laser applications [26, 31, 35]. The use of pulses, less than
20 ps, for LIBS has not been reported in the context of el-
emental analysis of solids, with a comparison to ns LIBS.
In a recent paper we described the use of a 1.3 ps laser for
LIBS of copper, steel and glass samples [36]. In this paper
we present additional LIBS results on copper, steel and
glass samples using both 1.3 ps and 140 fs laser pulses. It
is shown that background signals are lower compared to
ns laser excitation and that excellent results can be ob-
tained using a non-gated detector when ultra-short pulses
are used. Furthermore, the plasma dissipates quickly enough
that high pulse rates can be used to improve sensitivity.
Experimental
Dual-pulse LIBS system
The pre-ablation spark dual-pulse LIBS setup is shown schemati-
cally in Fig. 1. The experimental setup has been previously de-
scribed, and will be reviewed briefly [18]. Two Q-switched
Nd:YAG lasers were used for these measurements. Both lasers had
~ 7 ns pulses and were operated at 1064 nm, at a repetition rate of
5 Hz. The laser used for sample ablation, with approximately 100 mJ/
pulse, was directed normal to the sample surface and focused 1 to
2 mm beyond the surface by a 100-mm focal length lens. The air-
spark laser pulse, with approximately 210 mJ/pulse, was directed
parallel to the sample and focused by a 100-mm focal length lens
approximately 1 mm above the sample surface. This beam was fo-
cused to a point above the sample that coincided with the center of
the sample plasma that was generated by the ablation beam. How-
ever, for most measurements it arrived at the sample approxi-
mately 2.5 µs before the ablation pulse (a 2.5 µs pre-ablation
spark), forming an air spark above the surface, prior to any sample
ablation. This timing was found to be within the optimal range pro-
ducing large LIBS signal enhancements for all samples tested. The
effect of laser pulse timing was investigated by bringing in the pre-
ablation spark up to 1000 µs before the ablation laser pulse.
Emission was collected using 2-mm diameter optical fibers,
both at right angles, and axially to the ablation laser beam, as
shown in Fig. 1. The same lens that was used to focus the ablation
pulse onto the sample was also used to collect axial emission. The
optical fibers were coupled to a 0.25 m, f/4 spectrograph (Chromex
Model 250IS/RF) with a gated intensified charge coupled detector-
ICCD (Princeton Instruments, Model ITEA/CCD-576-S/RB-E)
with Model PG-200 pulser and Model ST-138 detector controller.
For laser pulse delay timing experiments, the detector gate delay
was typically 2.0 µs after the ablation laser pulse, and the gate
width was typically 0.5 µs. The detector gate delay and gate width
is indicated for each measurement. The gate delay time was typi-
cally 0.02 to 0.1 µs and was matched as closely as possible be-
tween the ps and ns experiments. However, due to the fast decay of
the ps and fs plasmas, the detector gate delay could not be matched
with the ns experiments. For the plots that show LIBS signal ver-
321
Fig. 1 Schematic diagram of pre-ablation spark, dual-pulse set-up
using fiber-optics for both side and top collection
sus time delay after the laser pulse, the standard deviation of the
LIBS intensity at each delay time was calculated by measuring five
replicate spectra taken from five different locations on the sample
surface, with no pre-shots used to prepare the surface of the sam-
ple. The same procedure was used to calculate the standard devia-
tion for the plots of LIBS signal versus laser pulse rate. Because of
the speed with which it ablated material, fs measurements were
made using the minimal number of laser shots. Plasma images of
Cu were acquired by imaging the plasma directly with the ICCD
using an AOTF tuned to the 521.8 nm Cu line. Scanning electron
microscope (SEM) images were used to examine the ablation
craters that were formed during measurement of the samples.
Ultra-fast laser systems
The ultra-fast LIBS studies are not directly related to the dual-
pulse studies. The purpose of the dual-pulse studies was to im-
prove the sensitivity of LIBS; whereas, the ultra-fast LIBS studies
were related to improving the precision of LIBS measurements.
The 1.3 ps laser system used for these studies has been previously
described [37]. Briefly, light pulses approximately 1.3 ps in length
were generated by a synchronously pumped dye laser, pumped by
a pulse compressed mode-locked Nd:YAG laser. These pulses
were amplified at 10 Hz by a chain of dye amplifiers to produce an
energy of approximately 1.0 mJ at 570 nm. The pulse energy sta-
bility was < 2%. The laser power was typically 1 mJ and the mode
quality of the laser varied significantly during the course of the ex-
periments. The fs laser system is commercially available. It con-
sists of a mode-locked Ti:Sapphire oscillator (Spectra Physics
Tsunami) pumped by a diode pumped, CW, Nd:YVO4 crystal laser
(Spectra Physics Millennia), and a regenerative high repetition-
rate chirped amplifier (Positive Light Spitfire Multikilohertz
Ti:Sapphire) pumped by an Intra-Cavity Doubled Nd:YLF Laser
(Positive Light Merlin). The system puts out ~ 1 mJ, ~ 140 fs pulses
at ~ 810 nm at pulse rates from 1 to 1000 Hz. The pulse energy sta-
bility is < 2%. The laser beam was focused on the sample at nor-
mal incidence using a 100 mm focal length lens.
Preparation of samples
The metal samples investigated were primarily composed of the
metal of interest. The low-carbon steel and copper samples used in
this work were obtained from an industrial supply company and
are of unknown purity. Yellow brass samples contained approxi-
mately 65% Cu and 35% Zn. Glass samples were prepared by The
322
Fig. 2 LIBS spectra (center),
plasma images (left) and abla-
tion crater images (a, and
b, right) using single-pulse
excitation (50 pulses, upper
images, and curve) and pre-
ablation spark dual-pulse
(50 pulse-pairs, lower images
and curve) excitation. The gate
width and gate delay times
were 0.2 µs and 2 µs, respec-
tively for the LIBS spectra.
The gate width and gate delay
times were 2 µs and 1 µs, re-
spectively for the plasma im-
ages

Savannah River Site Vitrification Facility and the preparation has magnitude of the effect. Figure 3 shows SEM images of
been previously described [38]. the ablation region for a brass sample consisting of ~ 65%
Cu and ~ 35% Zn. Again, greatly enhanced material re-
moval is evident when a pre-ablation spark is used (a)
Results and discussion compared to the use of single laser pulses (b). However,
whereas Cu is enhanced about the same amount in brass
The first report of enhanced emission using a pre-ablation
as in copper metal, the magnitude of the enhancement for
spark focused on metal samples [21], and recently, we ex-
Zn is significantly greater in brass than in zinc metal. It is
tended the technique to glass samples [38]. Figure 2 shows
interesting to note that the brass sample is mostly made of
LIBS results for a copper sample using single-pulse exci-
copper. Figure 4 shows single- (lower spectra) and dual-
tation (top images and spectrum) compared to dual-pulse
pulse (upper spectra) LIBS spectra for (a) Cu and Zn in
using a 2.5 µs pre-ablation spark (lower images and spec-
brass, (b) Cu in copper metal and (c) Zn in zinc metal us-
trum). The dual-pulse spectrum is enhanced ~ 40 times
ing side collection. The 578 nm Cu line is enhanced simi-
compared to the single-pulse spectrum. The increased
larly (~ 16 to 17 fold or 23 to 27 fold, using top and side
emission intensity is apparently a result of a larger plasma
collection, respectively) in both (b) pure copper and (a)
as can be seen by comparison of the single-pulse and dual-
brass samples. However, Zn shows a much larger en-
pulse plasma images. The radiance is about the same in
hancement in brass (~ 10 fold or 16 fold using top and
each case, as is the plasma temperature during the mea-
surement time. However, the radiant power is much higher
for the much larger dual-pulse plasma. The SEM image of
the ablation region shows greatly enhanced material re-
moval for the dual-pulse experiment. The reason for this
effect is not yet known but is likely a result of increased
coupling between the ablation pulse and the sample. Al-
though the pre-ablation spark does produce a subtle color
change on the sample surface, the effect is not the result of
a permanent change in the sample as the magnitude of the
enhancement decreases dramatically for long delay times
between the two pulses, and quickly disappears. It is also
not a simple thermal effect as both good conductors (e.g.,
copper) and thermal insulating materials (e.g., glass) show
similar large enhancements. Fig. 3 SEM images of ablation craters produced on brass using
Although large dual-pulse enhancements were seen for 100, 7-ns laser shots (b) and 50, 7-ns pulse pairs, in a pre-ablation
all samples studied, the matrix does have an effect on the spark setup (a), with pulses separated by 2.5 µs

Fig. 4 LIBS spectra of brass (a), copper metal (b) and zinc metal
(c) using single-pulse (lower curves) and dual-pulse (upper curves)
excitation. Note: Enhanced and single-pulse spectra are shown us-
ing the same y-axis. A 2.5 µs delay between pulses was used for
the pre-ablation spark, dual-pulse experiments. The Cu and Zn
lines appear at 578.2 nm and 636.2 nm, respectively. The gate
width and gate delay times were 1.5 µs and 2 µs, respectively for
the spectra shown
Table 1 Pre-ablation spark, dual-pulse enhancement for Cu and
Zn in brass, copper and zinc. Both top and side collection are
shown. The gate width and gate delay times were 1.5 µs and 2 µs,
respectively
Top collection Side collection
Cu Zn Cu Zn
Brass ~ 16 ~ 10 Brass ~ 27 ~ 16
Cu ~ 17 Cu ~ 23
Zn ~4 Zn ~9
side collection, respectively) than in pure zinc (~ 4 fold or
9 fold using top and side collection, respectively) and is
closer to Cu in magnitude in the brass sample. Table 1
shows a summary of the enhancements for Cu and Zn in
brass, pure copper and zinc using both top and side col-
lection. The enhancements are significantly larger, approx-
imately 2X, for side collection. This effect might be caused
in part by the limited field of view of the fiber, which might
not collect emission equally from all parts of the plasma.
In an attempt to reduce this effect the side-collection fiber
was usually optimized for single-pulse excitation.
Figure 5 shows dual-pulse enhanced LIBS spectra (up-
per) for a sample of steel, using a 2.5 µs pre-spark com-
pared to single pulse excitation (lower). Most of the emis-
sion lines shown are from Fe. The enhancement is ap-
proximately 28 fold based on the 404.6 nm Fe line. The
Fe lines were also used to measure the temperature of the
plasma for both single- and dual-pulse excitation using a
previously described method [38, 39]. In each case the
plasma temperature was approximately 12,000–13,000 K,
during the measurement time. Similar plasma tempera-
tures were measured for iron-containing glass samples.
323
Fig. 5 LIBS spectra of steel showing Fe lines using single-pulse
(lower curve) and dual-pulse (upper curve) excitation. Note: En-
hanced and single-pulse spectra are shown using the same y-axis.
A 2.5 µs delay between pulses was used for the pre-ablation spark,
dual-pulse measurement. The gate width and gate delay times were
0.5 µs and 2 µs, respectively for the spectra shown
For most samples the temperature drops bi-exponentially
after the laser pulse, when ns-pulsed excitation is used.
The ultra-fast LIBS studies are not directly related to
the dual-pulse studies. The purpose of the dual-pulse stud-
ies was to improve the sensitivity of LIBS; whereas, the
ultra-fast LIBS studies were related to improving the pre-
cision of LIBS measurements. The use of ultra-short laser
pulses seems to offer many advantages for LIBS com-
pared to the use of ns laser pulses. For ultra-short pulses,
< 20 ps, it has been shown that the thermal diffusion
length is smaller than the laser spot, and that the threshold
power at which ablation occurs is more reproducible [25].
As a result, short laser pulses produce less thermal dam-
age around the ablation region and form very precise
holes. The pulse peak power is also high enough that ma-
terial is removed without melting, going directly to a va-
por or plasma phase, greatly reducing material re-deposi-
tion. It has been shown that with ultra-short pulses, the
plasma is formed by direct photo-ionization of the mater-
ial through a multi-photon process [27]. This is unlike the
case of ns laser excitation where melted material forms in
the ablation region and ablated material is ionized by elec-
tron-ion collisions [27]. In the case of a ns LIBS experi-
ment, the laser pulse is long enough to re-heat the result-
ing plasma, but the process is difficult to predict because
the laser continues to ablate material while being shielded
from the sample by the plasma. For the ps LIBS experiment,
the laser pulse is so short that it does not interact with the
plasma [25]. Also, the energy is typically high enough to
directly ionize both conducting and wide band-gap mate-
rials like ceramics, and thus is not limited by the material.
Figure 6 shows the ablation region for copper using 50,
1.3 ps pulses (a) compared to 50, 7 ns pulse (b). The holes
are of similar diameter, but the hole formed using the ns
laser pulse shows a large amount of re-deposited material
around it and considerable melting. The edges of the
324

Fig. 6 SEM images of ablation craters on copper using 50, 1.3-ps

laser pulses (a) compared to using 50, 7-ns pulses (b)

Fig. 8 Intensity of the 510.5 nm Cu line (open squares) and back-

ground (open circles) versus decay time after the laser pulse using
1.3 ps (a) and 140 fs (b) excitation. The gate width was 0.02 µs in
each case. The error bars show the standard deviation of 5 replicate
measurements

Fig. 7 LIBS spectra of Cu lines in a copper sample as a function

of delay time after the 1.3 ps excitation pulse. The gate width was
0.02 µs for all spectra. The delay times were (a) 0.06 µs, (b) 0.18 µs,
(c) 0.30 µs and (d) 0.50 µs

crater are also not well defined. In contrast, the hole

formed using the ps pulses has extremely well defined
edges and shows no evidence of material re-deposition or
melting. Although not as clear from these images the as-
pect ratio is also very high for this hole.
The plasma generated using 1.3 ps and 140 fs laser
pulses is qualitatively different from the plasma generated
using ns pulses. The plasma generated using 1.3 ps and
140 fs pulses is much smaller than a ns-excited plasma,
most likely a result of the lower threshold required for the
Fig. 9 Non-gated (upper curve) and gated (lower curve) LIBS
former, and plasma re-heating for the latter. The power spectra of Cu using 140 fs laser pulses. Both spectra were acquired
threshold for LIBS using a ns laser is many times higher using 10 laser pulses. The exposure time was 1 s for the non-gated
than using a ps or fs pulse. The ns laser pulse interacts spectrum. The gate width and gate delay times were 1 µs and 0.1 µs,
with the plasma causing re-heating and expansion. This is respectively for the gated spectrum. The non-gated measurement is
noisier because of high thermal noise in the detector
not observed using ultra-short pulses because the pulse is
too short to interact with the plasma. Figure 7 shows LIBS
spectra of copper at different delay times after a 1.3 ps

Fig. 10 LIBS intensity for the 510.5 nm Cu line versus the pulse
rate of the 140 fs laser. Each measurement was made by integrat-
ing the signal produced by 100 laser shots. The exposure time is
determined by the pulse rate (i.e., 0.1 s for 1000 Hz, and 10 s for
10 Hz). The error bars show the standard deviation of 5 replicate
measurements
laser pulse. Several things are evident in these spectra.
The background is relatively low within 50 ns of the laser
pulse, relative to ns excitation, and the atomic lines are
well defined within about 200 ns [36]. The atomic line in-
tensity also decays very quickly compared to ns excita-
tion. The background is typically much higher using ns
pulses and the atomic lines are not as narrow until later
delay times (see Fig. 8).
Figure 8 a shows a comparison of the Cu 510.5 nm
atomic line (open squares) and the background (open cir-
cles) intensity as a function of time after the 1.3 ps laser
pulse. This further illustrates the low background observed
using ultra-fast pulse excitation, even at very early times,
and the very rapid decrease of the atomic line intensity.
Interestingly, the background(open circles) is significantly
Fig. 11 (Left) Near-collinear,
dual-pulse fiber-optic probe
design. (Right) SEM image of a
lead sample after excitation us-
ing 100 pulse pairs. The circles
denote the areas illuminated by
each fiber. The second laser
pulse, plasma re-heating pulse,
was on the right
325
higher, though still low compared to ns excitation, using a
140 fs laser pulse and top collection as shown in Fig. 8 b.
The atomic line intensity decays at least 20 times faster
using ultra-short pulse excitation compared to 7-ns pulse
excitation [36].
The relatively low background observed when using ps
and fs excitation suggests that it might be possible to ob-
tain LIBS atomic-line spectra without gating the detector,
and that the plasma might dissipate quickly compared to
excitation with a ns laser pulse. This is demonstrated in
Fig. 9 (upper curve) which shows a Cu spectrum obtained
using a 140 fs laser pulse without gating the detector,
compared to the spectrum obtained with a gated detector
(lower curve). The non-gated spectrum is a 1-s exposure
using a 10 Hz laser pulse rate (e.g., 10 total laser pulses).
The gated spectrum was also run at 10 Hz but using a 1 µs
gate width and 5 accumulations (e.g., 5 laser pulses). The
gated spectrum was scaled 2 times, for direct comparison
with the non-gated spectrum. As expected, the non-gated
spectral intensity is higher, though the signal-to-back-
ground is approximately 10 times worse for the non-gated
spectrum compared to the gated spectrum. The high noise
level on the non-gated spectrum is partly a result of high
thermal noise in the ICCD detector and does not represent
the noise of the emission spectrum. This was determined
by detector tests after these spectra were acquired. Both
spectra were collected using top collection which was shown
in Fig. 8 b to be the worst case condition for obtaining low
background signals. Even so, the non-gated spectrum
shows relatively low background compared to 7-ns laser
pulse excitation [36]. However, overall the non-gated
spectrum is superior in terms of noise level and line width.
We have found, that for ns laser pulse excitation, the
plasma dissipates relatively slowly and interferes with
326
subsequent laser pulses, limiting the useful pulse rate to
~ 10 Hz [11]. The ps and fs decay curves shown in Fig. 8
suggest that the plasma might dissipate more rapidly us-
ing ultra-short pulses. Rapid dissipation of the plasma
would make it possible to use higher laser pulse rates and
thus obtain a sensitivity increase, for a given measure-
ment time. In the case of fs excitation, we have found that
extremely high pulse rates can be used advantageously to
increase the signal for a given measurement time. This is
demonstrated in Fig. 10 which shows the integrated inten-
sity of the 510.5 nm Cu line for 100 laser pulses, as a
function of the laser pulse rate. Interference of subsequent
pulses by the plasma would show up as a decrease in the
signal with increasing pulse rate. The experiment was car-
ried out for a fixed number of laser pulses to control the
amount of material ablated during each experiment. In
this way, intensity variations caused by changes in hole
depth are minimized. Figure 10 shows that there is no sig-
nificant change in the signal for 100 laser shots at rates
ranging from 5 to 1000 pulses per second. Thus, the use of
high pulse rates is useful for increasing the sensitivity of a
LIBS measurement with fs excitation, for a given mea-
surement time.
The use of fiber-optics for LIBS measurements has
been described [9–13]. However, few dual-pulse LIBS
measurements have been described using optical fibers
[13, 19]. Figure 11 shows a fiber-optic LIBS probe design
for near-collinear, dual-pulse LIBS measurements. In the
case of collinear dual-pulse LIBS, a laser pulse is first
used to ablate material and form the plasma, and then the
plasma is re-heated by the second laser pulse to increase
the emission intensity. Although collinear dual-pulse
LIBS doesn’t show enhancements as large as pre-ablation
spark dual-pulse LIBS, it has been shown that the use of
dual-laser pulses can be used to enhance emission signals
and lower detection limits [16–24]. We have reported en-
hancements between 2 and 7 fold for collinear dual-pulse
Fig. 12 Collinear dual-pulse LIBS spectrum (upper inset spec-
trum) and single-pulse LIBS spectrum (lower spectrum) using the
fiber-optic dual-pulse probe for lead using 7-ns laser pulses. The
signal enhancement versus delay time between the pulse pairs is
shown by the open circles. The gate width and gate delay times
were 0.2 µs and 1.5 µs, respectively. The error bars represent +/-
one standard deviation that was calculated using 5 measurements
excitation of lead and copper, respectively [40]. Similar
results are obtained using the dual-pulse fiber-optic probe.
Figure 12 (inset) shows lead LIBS spectra for single-
(lower spectrum) compared to collinear, dual-pulse exci-
tation. In this case, the delay time between the laser pulses
was 20 µs. As shown in this figure (open circles), the
magnitude of the enhancement is highly dependent on the
delay time between the laser pulses, increasing rapidly
from 0 to 20 µs then dropping off slowly at later delay
times.
Conclusions
Pre-ablation spark dual-pulse LIBS has been shown to
produce enhancements up to 40X. The temperature and
spectral radiance of the plasma is similar to that observed
using a single laser pulse. This new dual-pulse technique
should prove useful for analysis of solid materials with
improved sensitivity. Future studies are being designed to
understand the mechanism of enhancement and to extend
the technique to the measurement of solutions.
In an independent study, LIBS spectra using ultra short
laser pulses show relatively low background emission and
rapid decay of atomic line intensity compared to ns exci-
tation. Non-gated LIBS spectra using 1.3 ps and 140 fs laser
pulses have been shown. In the case of fs laser pulse exci-
tation, high laser pulse rates, up to 1000 Hz, are shown to
increase the LIBS signal. Ultra-fast excitation should
prove useful in improving the precision of LIBS measure-
ments. Further studies are needed to determine if the en-
hanced precision is worth the increased complexity of the
laser system.
Acknowledgements SMA would like to thank the U.S. Depart-
ment of Energy for support of this work under grant number
DEFG0796ER62305, and we also express thanks to the Office of
Naval Research for support of this work under grant number
N0014-97-1-0806. The ps laser system used for this work was sup-
ported by the National Science Foundation under Grant No. CHE-
9809719 to MAB. We would also like to thank The Savannah
River Vitrification facility for preparation of the glass calibration
samples, and Hugh Hubble for help with the laser system.
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