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