Technical Papers

CMA 2010
The 42nd Annual Conference and Exhibition
September 12 16, Trail Rossland, BC

Laser Induced Breakdown Spectroscopy:

A Unique and Complementary Elemental
Analysis Tool for a Wide Range of Industrial and
Research Applications

Scott W. McGeorge, Transition Technologies, Inc.,Toronto, ON, Canada

www.transition.ca
Steven G. Buckley, Photon Machines, Inc., Redmond, WA, USA
www.photon-machines.com
 Laser-Induced Breakdown Spectroscopy (LIBS) uses a
laser microplasma to excite atomic emission

Laser-induced Line position provides

plasma
. species identification.
Line intensity provides
species concentration.
Pulsed
laser Atomic
emission
collection
Fiber
optic

Spectrometer Detector

F. Ferioli and S.G. Buckley, Measurements of Hydrocarbons using

Laser-Induced Breakdown Spectroscopy, Combustion and Flame.
 Elements in RED among those measured with
LIBS and found in the literature (courtesy ARL)

1 2
H He
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
87 88 89
Fr Ra Ac
58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
90 91 92 93 94 95 96 97 98 99 100 101 102 103
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Example: LIBS spectra of different coals
 Many applications for LIBS have been
developed in the last twenty years

Analysis of
archeological
samples
Analysis / typing of
metal alloys
Measurement of
incinerator exhaust
(aerosols)
Geological samples
Elemental surface LIBS is planned as a diagnostic for a Mars
Rover expedition set to launch in Sept. 2011
maps
Depth profiling
 Benefits of LIBS over other techniques

Little or no sample preparation required

Surface cleaning can be done in place

Powders do require pressing

Spot size control from 5 microns 2 mm allows

variation between macro and microanalysis

Scanning ability, integration, depth profiling

Low-Z elements, particularly Li, Be, B, C, N, O, Na, Mg,

Al, and Si, which can all be difficult with other
methods

Good comparative detection limits, e.g. generally 1-100

ppm
 Building a LIBS system: Hardware choices

Laser wavelength
Typically Nd:YAG lasers are used as they are
low-maintenance and low $$$/joule pulsed
lasers
1064 nm fundamental couples into plasma
better
Short wavelength (e.g. 266 harmonic) ablates
material better
Dual pulse option
Czerny-Turner + ICCD

Sensitivity
Spectrometer / detector
Gated detectors reject initial continuum from Echelle + ICCD
plasma
Intensified detectors have much more gain Broadband diode array
than non-intensified detectors, and are more
accurately gated Resolution
Broadband spectrometers allow associations
between elements that may have spectrally-
separated lines
 Application: Rapid material identification

Broadband
spectra can be
used to quickly
match materials
Many, many
lines
Useful for
sorting,
checking
inventory,
ascertaining
quality
 Example: Identification of Stainless Steel

5 different types of
stainless steel
10 shots on each
surface
10 Hz, 100
mJ/pulse, 1064 nm
Nd:YAG
Spectra collected by
an echelle
spectrometer
Ratios 304 316 416 321 410 Simple line ratios
Cr/Fe 0.89 0.83 0.48 1.00 0.98 can be used to
Mn/Fe 1.00 0.88 0.49 1.00 0.81 discriminate
Mo/Fe 0.55 1.00 0.21 0.49 0.45 samples
Ni/Fe 0.73 1.00 0.26 0.62 0.16 PCA is even more
Ni/Cr 0.67 1.00 0.45 0.51 0.14
sensitive
 Application: Depth profiling

Successive LIBS
pulses provide
depth profiles
Example: thin
film
interrogation
266 nm Nd:YAG,
single shots, ~
10 mJ/pulse
Czerny-Turner
spectrometer,
UV line ratio of
two light
elements
 Another method of depth profiling for moving substrate:
variation of pulse energy

Successive pulses burrow more

deeply integrating previous
pulses with new material
Balzer et al., Anal Bioanal Chem
(2006) 385: 225233
 Standard calibrations or chemometric methods can be
used to classify types or quantify elements

Typical spectra are rich 45000

with information
Al
40000
Typi cal gems tone
Classification methods
35000
spectrum (beryl ) taken
such as PLS-DA or 30000
Al
wi th a single laser shot
SIMCA can be used to 25000
using a Photon Ma chines
group data 20000
Insight s ys tem

Standard peak analysis,

Be Be
15000

peak ratios, or
statistical/chemometric
10000
Mg Na
Be
Mg

methods can be used 5000

Na Li

for calibration
Al Ca
H
0
300 350 400 450 500 550 600 650 700

Geological Example
 Calibration Curves for Chromium
6.0E-02
y = 1.93210-3x + 4.31610-3
5.0E-02 R = 0.992
Intensity ICr/TL (a.u.)

4.0E-02

3.0E-02
Normalization to plasma
2.0E-02
Chromium peak at 397.67 nm
1.0E-02
Linear
0.0E+00
0 5 10 15 20 25 30
Similar R2 to internal
Chromium Concentration (wt %) standard
7.0E-01
y = -0.827x 2 + 1.507x + 0.031
Intensity Ratio ICr/IFe (a.u.)

6.0E-01 R = 0.995

Fe Internal Standard
5.0E-01

4.0E-01

3.0E-01 Iron line at 404.58 nm used

2.0E-01
for normalization
1.0E-01

0.0E+00
0 0.1 0.2 0.3 0.4 0.5 0.6

Concentration Ratio [Cr]/[Fe]

Data from Stipe, Buckley et al., Photon Machines, Inc.,
Applied Spectroscopy 64 (2) p154. (Feb 2010)
 New Product: Insight LIBS

266 nm or 1064 nm
single-laser system for
microanalysis
5 micron 2mm spots
with 266 nm
wavelength
Computer-controlled
stages
All enclosed, rugged
Coaxial video
Standard with echelle
spectrometer or
multichannel CCD array
Debut of new
Chromium software
Chromium software for machine control
 addLIBS analysis software allows method
development and automation

Identify spectral
features using
NIST or user
library
Build a method
with calibration
data
Automate and
repeat methods
Advanced
calibration
techniques such
as multiple linear
regressions and
PLS included
 Chemometric methods applied to LIBS

Multivariate statistical methods for

classification and quantification
SIMCA, PCA analysis for classification by
type
PLS regression, etc., for more quantitative
results
Benefits
Trainable calibration and classification
methods
Highly sensitive due to multivariate nature
Caveats
Must understand analysis data set to
properly set up methods
 Chemometric methods applied to LIBS

We were among the

first to apply
chemometrics to LIBS
Now collaborating with
Infometrix of Bothell,
WA

J.D. Hybl, G.A. Lithgow, S.G. Buckley, Laser-Induced Breakdown

Spectroscopy Detection and Classification of Biological Aerosols
Applied Spectroscopy 57 (10), pp 1207-1215, (2003).
 LIBS for mining safety: US NIOSH

Preliminary LIBS results

1.4E+05
Concern: silicosis y = 324.07x + 23370

US National Institute
R = 0.9785
1.2E+05

for Occupational
Health and Safety
1.0E+05

LIBS Signal (a.u.)

Develop system for 8.0E+04

automatic collection 2.5E+04

Blank
Si251 (18ug)

of dust onto filters

6.0E+04 2.0E+04
Si507 (53ug)
Si7513 (88 ug)
Si10019 (108ug)
Si20028 (217ug)
Si30034 (326 ug)

LIBS Intensity (a.u.)

Analyze filters with
1.5E+04

4.0E+04
1.0E+04

LIBS for rapid assay 2.0E+04

5.0E+03

Ongoing product 0.0E+00

287 287.5 288 288.5 289

development at
Wavelength (nm)

0.0E+00

Photon Machines
0 50 100 150 200 250 300 350
Deposited Silica Mass (g)

Detection limit 0.7 g/cm2 Si

Phosphate mining applications

Rapid detection of
phosphorous and
nitrogen in fertilizer
is crucial
Product spec and
blending applications
LIBS provides a
relatively quick
assay
 LIBS analysis procedure

Sample 1 3 5 7 9 11 13 15 17 21
P2O5
(%) 46.06 46.74 47.08 47.78 48.73 49.08 49.76 50.1 50.92 51.86

N (%) 17.81 17.09 16.48 15.72 15.01 14.43 13.95 13.09 12.38 10.9

% P2O5 %N
53 19

Photon Machines Insight 52 18

was used to interrogate

Nitrogen Concentration (%)

17
51

P2O5 Concentration (%)

pressed pellets of fertilizer 16
that had been ground to ~ 50

50-100 microns in a mill 49

15

5 analysis points were 14

acquired on each of 10
48
13
pellets of varying N and P 47
12
concentration, taken from 46
samples shown at right 11

45 10
0 5 10 15 20 25
Sample number
 Insight LIBS system parameters

30000
25 400 micron
spots interrogated 25000

2 cleaning shots
followed by 10 20000

Intensity (arb. units)

measurement 15000
shots at each point
Intensified CCD 10000

camera with Phosphorous Nitrogen

5000
echelle
spectrometer on- 0
board 200 300 400 500 600 700 800
Wavelength (nm)

Ample spectral information in broadband LIBS spectrum

 LIBS Spectral Model:
Using all data to predict P

Chemometric
model can be
very accurate
Plot shows
predicted versus
known values

Prediction of Phosphorus using all data points

 LIBS Spectral Model:
Using all data to predict N

Prediction of Nitrogen using all data points

Using a limited data sample (2 points) to predict
P and N in 3 unknown samples using LIBS

52 smp49 smp4
smp5
smp48 18
smp3
smp8
smp9
smp43
smp50 smp10
smp44 smp13
smp38 smp45 smp14
smp34
50 smp40 16 smp15
smp20
Predicted Y

Predicted Y
smp35 smp18
smp30 smp33 smp29
smp39 smp24smp19
smp25
smp23
smp28
smp28
smp23
14 smp33 smp25
48 smp24
smp19 smp29 smp39 smp35
smp30
smp20
smp18
smp15 smp40 smp34
smp14 smp45
smp44
smp13 12 smp43 smp38
smp10
smp9
smp8 smp50
46 smp3
smp5
smp4 smp48
smp49
4 4

46 48 50 52 12 14 16 18

Measured Y Measured Y

Predicted versus measured P Predicted versus measured N

Only two samples from each set of 5 were

used to build the model which was in turn
exercised to make predictions
 Questions?

Thank you for your

attention!