LIBS and LA-ICPMS for structured materials
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Transcript of LIBS and LA-ICPMS for structured materials
Plasma Application Group, April 29, 2013
Real-Time Determination of Compositional Profiles in Structured Materials Using Laser Ablation and
LA-ICPMS Alexander A. Boľshakov, Jong H. Yoo, Jhanis J. González,
and Richard E. Russo
Plasma Application Group, April 29, 2013
Laser ablation in applications
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• Micro machining • 3D texturing and sintering • Chemical analysis
RIKEN Review No. 50 (January, 2003): Focused on Laser Precision Microfabrication (LPM 2002)
Plasma Application Group, April 29, 2013
Laser ablation chemical analysis
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Laser
Data Display
Mirror
Objective Lens
Fiberoptic Cable
Focus Lens
Plasma Sample
Spectrograph XYZ Stage
LIBS principle of operation:
• Simple, rapid, real-time • Any kind of sample • No sample preparation • High spatial resolution ~10 µm • Mapping, depth-profiling
Laser-induced breakdown spectroscopy (LIBS)
RT100 RT100
λ, nm 266 532 1064
Plasma Application Group, April 29, 2013
Commercial LIBS and LA-ICPMS
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• Isotopic & elemental analysis • Simple, rapid, real-time • Any kind of sample • No sample preparation • High spatial resolution • Minimum fractionation • Mapping, depth-profiling
RT100 RT100 J100-UV J100-UV
femto-LA–ICPMS, 100 kHz ns-LIBS, 20 Hz
www.appliedspectra.com
λ, nm 266 532 1064
λ, nm 343 1030 (150 µJ)
Plasma Application Group, April 29, 2013
Tandem LA–LIBS: OES & ICPMS
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• Emission and MS simultaneously • Normalization of isotopic ICPMS • All elements including H, C, N, O • Modular, easily upgradable • Up to Two LIBS spectrographs • Easy upgrade to fs-LA–ICPMS
LA–LIBS, Nd:YAG, 5 ns, 20 Hz
www.appliedspectra.com
λ, nm 213 4.5 mJ 266 25 mJ 532 55 mJ 1064 100 mJ
• Isotopic & elemental analysis • Simple, rapid, real-time • Any kind of sample • No sample preparation • High spatial resolution • Rapid mapping, depth-profiling
Plasma Application Group, April 29, 2013
Line broadening and shift
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284 285 286 287 288 289 290 291 292 2930.0
5.0x103
1.0x104
1.5x104
2.0x104
150ns delay
50ns delay
30ns delay
10ns delay
Inte
nsity
(a.u
)
Wavelength λ (nm)
• Broadening: Stark, Doppler, collisional, resonant
• Continuum radiation: • Free electron-ion recombination • Bremsstrahlung
Plasma Application Group, April 29, 2013
Depth profiling analysis
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• Depth resolution ~ 20 nm
Solar cell structure e-Storage substrate
Wavelength, nm
236 238 240 242 244 246 248 250 252 254 256 258 260NI
(II)
239.
9nm
Ni (I
I) 24
1.6n
m
Ni (I
I) 24
3.7n
m
Ni (I
I) 25
1.2n
m
P (I)
253
.5nm
Ni (I
I) 25
4.3n
m
236 238 240 242 244 246 248 250 252 254 256 258 260
NI (I
I) 23
9.9n
m
Ni (I
I) 24
1.6n
m
Ni (I
I) 24
3.7n
m
Ni (I
I) 25
1.2n
m
P (I)
253
.5nm
Ni (I
I) 25
4.3n
m
Uniformity of 150 nm NiP layer
Wavelength, nm
Aluminum
NiP
Plasma Application Group, April 29, 2013
Discrimination of materials
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Raw materials: 10 steel samples classified using PCA and PLS-DA
Ni Ni
Mo
• λ = 1064 nm • ppm sensitivity • fast discrimination
• Not possible by XRF • Too slow by ICP
Plasma Application Group, April 29, 2013
Quality of fiberglass panels
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300 400 500 600
l th ( )
Ti Ca C H Na CN
PCA discrimination of high vs low quality of fiberglass coatings
High-quality samples consistently demonstrate similar spectra
•
•
High quality
Low quality
Laser 25 mJ Spot size 300 µm
Lateral steps 500 µm
Plasma Application Group, April 29, 2013
High-lead vs. low-lead
12 different solders tested
(RoHS limit <0.1% Pb)
Com
pone
nt P
C1
Principal component PC2
Discrimination of solders
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Thin plated solder leads and solder balls in chips
• Library spectra stored
Plasma Application Group, April 29, 2013
LIBS calibration for Pb
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Quantitative analysis of electrical solders and solder platings
Pb detection limit <10ppm
1E-4 1E-3 0.01 0.1 1
PBSN DATA2PBSN 4% silver slver bearing 5% antimony 2% silver lead free solder 1
Pb/S
n LI
BS In
tens
ity (a
.u.)
Pb/Sn
<10 sec per sample
Plasma Application Group, April 29, 2013
Lead in paint and toys
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404 406 408 410
Cu
Pb (4
05.7
5 nm
)
hg (4
04.6
6 nm
)
Wavelength (nm)
Standard sample / calibration for Pb
Pb
0.1 1
~0.15mg/cm2
~1.85% or 18500 PPM
Orange truck
test day 1 test day 2 Orange truck Linear fit
Pb surface concentration (mg/cm2)
0 5 10 15 200
10000
20000
30000
40000
50000
60000
70000 Base layerPaint layer
Pb high Pb low
Pb e
mis
sion
(a.
u.)
Consecutive laser shot number CPSC rule: 300 ppm
90 ppm in paint
Depth resolution ~ 0.5 µm
Detection limits: 15 ppm Pb (0.1 µg/cm2)
13 Plasma Application Group, April 29, 2013
200 300 400 500 600 700 800 900
Ca (393, 396 nm)
O (777 nm)H (656 nm)C (247 nm) Icy inhibitor Diesel Lubricity improver Cetane boost NISTdeisel
Norm
alize
d LI
BS E
miss
ion
Wavelength (nm)
C H O
300 400 500 600 700 800
0.0
0.5
1.0
CN CN
N
HO
Sodium (Na)
Norm
alize
d LI
BS In
tens
ity
Wavelength (nm)
Valvoline Chevron Mobil Shell
H
CN
C2
Ca
280 290 300 310
200
400
600
800
1000
gate delay=0.5 µsgate width= 5 µslaser energy=40mJ
Mg
Inte
nsity
Wavelength (nm)
Clean motor oil Used motor oilMg
10W-30
Four oil brands Clean vs used
Contaminant detection level: ~40 ppm (may include particulates)
PLS analysis discriminates fuels and oils
Motor oil, diesel and additives
Plasma Application Group, April 29, 2013
High repetition LA-ICPMS
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0 50 100 150 200 250 300 350 400102
103
104
105
106
107
108
109
Time (sec)
27Al 232Th 238U
Laser on
Laser off Glass samples
2 mm (30 s)
Concentration of 232Th, 238U – 37 µg/g Laser repetition rate – 20 kHz (λ=343 nm) Stage moving speed – 20 mm/s
X~10µm
Z~5µm
NIST-612
X~5µm
15 Plasma Application Group, April 29, 2013
232Th, 238U intensities and their ratio at repetition rate of 20kHz
102
103
104
105
106
107
232Th 238U
0.00.20.40.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.0
232Th/238U 0.71 +/-0.035, RSD%=5
232Th/238U
103
104
105
106
107
232Th 238U
0.00.20.40.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.0
232Th/238U 0.71 +/-0.035, RSD%=5
Quasi-continuous LA scanning
16 Plasma Application Group, April 29, 2013
1E-4 1E-3 0.01 0.1 1104
105
106
107
108
Log Y = 8.045 + 1.043 Log XR = 0.9985
208Pb
Concentration (%)
λ = 343nm Laser energy ~0.1 mJ Fluence ~20 J/cm2 Spot size ~ 25µm Repetition rate 0.1 kHz Scan speed – 0.1 mm/s
Quantitative LA-ICPMS results
• Lead in zinc alloys • Linear calibration
Plasma Application Group, April 29, 2013
Correlation of LIBS and LA-ICP
A. Fernandez, X.L Mao, W.T. Chan, M.A. Shannon, R.E. Russo, “Correlation of spectral emission intensity in the inductively coupled plasma and laser-induced plasma during laser ablation of solid samples” – 1995
LA-ICP-OES
LIBS
Plasma Application Group, April 29, 2013
Conclusion
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• Fast (seconds)
• Sensitive (ppm, ppb)
• No sample prep • Elemental, isotopic • Organic and inorganic • Universal for any sample • Lateral and depth profiling • Commercially available models
LIBS, LA-ICP-MS in tandem
~3 µm; ~10 nm electronics optical devices protective coatings pharmaceutical coatings micro-mechanical, MEMS new modified materials
Plasma Application Group, April 29, 2013
Thank you
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www.appliedspectra.com