Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material...
Transcript of Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material...
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Material characterization with TOF-SIMS
Part 1: General- secondary ion mass spectrometry- time-of-flight mass spectrometry- instrumentation- general spectral features
Part 2: Applications- spectroscopy of complex
materials- imaging examples
Jukka LausmaaDepartment of Chemistry and Materials Technology, SP Swedish National Testing and Research Institute, Borås, Sweden
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TOF-SIMS is a mass spectrometric technique
Prerequisites for mass spectrometry:(i) free molecules in gas phase(ii) molecules in an charged state (measure m/z)
This can be achieved by, for example:thermal desorption, field emission, laser ablation, electrospray, electron impact, chemical ionization, plasmas, matrix assisted laser desorption/ionization, …
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SIMS: secondary ion mass spectrometry
Primary ions Secondary ions(~1-50 keV)
Solid
Sputtering
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Sputtering process
• Primary ion → collision cascade- primary recoils- secondary recoils
• Primary recoils cause sampledamage thoughout ion track
• PI’s implanted in material• Secondary recoils
→ particle emission from surface(sputtering)
→ surface damage
PISputtered particles- atoms and clusters- molecules and fragments- neutrals and secondary ions- electrons
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Important numbers and consequences
Sputter yield, Ys = removed particles / PI→ typically 1-10 @ 10 keV→ limit for non-destructive analysis
Secondary ion yield, YSI = secondary ions / PI
→ can vary from 1 – 10-6
(depends on ionization energy and matrix effects)→ quantification difficult
Large number of secondaryrecoils with low energy:→ emission depth ≤3 monolayers (high surface sensitivity)→ excited region diam. 0.3-10 nm (dependent on binding energy)→ low energy distribution (influences mass resolution)
- elements (1 - 5 eV, Thompson)- molecules (0.1 - 0.5 eV, M-B)
PISputteredparticles
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Dynamic SIMS
• High PI intensity• Beam damage• Analysis at continuously increasing depth
Main applications:• Bulk analysis (trace elements)• Depth profiles (e.g. surface films, dopant profiles)• Elemental imaging (e.g., grain boundaries, trace
elements in biological samples)
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Static SIMS
Number of particles removed from surface duringmeasurement should be negligible:
Typically 1014 – 1015 atoms cm-2 in one monolayer (ML)→ Primary ion dose density (PIDD) ≤1013 ions cm-2
Examples: Analysis area PI current Time100 x 100 µm2 1 pA ~10-100 s10 x 10 µm2 0.1 pA ~1-10 s
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Detection limits
Typically 1014 – 1015 atoms or molecules cm-2 in monolayer (1 ML)
Assume sputter yield, YSI = 1 and secondary ion yield YSI = 10-4
Analysis area Atoms/ML Secondary ions formed100 x 100 µm2 ~1010 ~106
10 x 10 µm2 ~108 ~104
→ static SIMS with high detection sensitivity requiresmass analyzer with high transmission
→ time-of-flight (TOF) analyzer
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Ion sourcesGa+ liquid metal ion source: High focus and intensityAu+
x liquid metal ion source: Higher sputter yields, similar focusBi+x liquid metal ion source: Present state-of-the-art
Cs+ liquid metal ion guns: enhances negative SI yields, poor focus
Electron impact guns (poor focus):
Ar+: general purposes, ion etching (depth profiling)
O2+: enhances positive SI yields
SF5+: enhanced yield for large molecular ions
shallow depth profiling (less ion mixing)
C60+ : enhanced yield for large molecular ions
shallow depth profiling (less ion mixing)depth profiling of organics
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Time of flight mass spectrometer
Sampleholder
Extractionelectrodes
Flightpath
Ion detector
TriggerSignal
Photodiode
Computer
For details, see for example:R.J. Cotter, Time-of-Flight Mass SpectrometryACS Symp. series, Vol.549 (1994)
Ion detector
Pulsedlaser
Variableattenuator
Mirrors
Lens
Y
Electrostaticreflector
U(>20 kV)
r e f l
V1(20 kV)
V2
mz = a t + b
2
a, b = constants(calibrated by twoknown masses)
Time0
Coun
ts TOF spectrum
Constant kinetic energyfrom acceleration field:
E = = z U
Flight time:
t =
=
k
2
mv2
2
Lv
2
2
mz
2 U tL
2
2
Pulsed ion beam
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Advantages of TOF-analyzer
• Unlimited mass range(in practice limited by ion formation and ion stability)
• High mass resolution; M/∆M (FWHM) > 10 000(single mass resolution at 10 000 amu)
• High accuracy (calibration dependent); - absolute mass error typically 10-3 amu for <100 amu- relative errors in 10 ppm range
• High transmission (parallell detection, no filtering)
Drawback:
Pulsed measurement (low duty cycle)low signal intensities (compared to other MS)
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High resolution mass spectrum (m/z = 30)
29.95 30.00 30.05
3x10
0.5
1.0
1.5
2.0
0
30Si
29SiH
28SiH2
CH2O
CH4N13CCH5
Silicon wafer, as rec.8 keV Ar+
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Pulsedion gun
secondaryions
ion detector
HV (+/-)
~10 nm
primary ions(Ga , Cs ,Ar , In , O , SF )
+ + +
+ + +
5
atomicions
molecularions
~1 nm
A+
C+
ABC+
AB+
B+
mass filter
extractor/ion opticsU
a c
ABC
Vacuum
TOF-SIMSTime-of-flight secondary ion mass spectrometry
Static SIMS: Pulsed primary ion beam, dose <10 cm (surface layer not removed)Dynamic SIMS: Continuous ion beam, analysis at increasing depths (depth profiling)
TOF: Method for mass filtration (measurement of flight time)
1 2 - 2
8t (m/z)1 / 2
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te1. Surface spectroscopy (static SIMS):• High surface sensitivity (information depth 1-3 molecular layers)• All elements, incl. isotopes are detected• High mass resolution gives specific chemical information• Low detection limits (% of monolayer down to ppm-ppb)
2. Microscopy (imaging):• Submicron lateral resolution• Analysis of composites, particles, fibres and microfabricated materials• Imaging of lateral distributions at surface or in cross sections
3. Depth profiling (dynamic SIMS):• Controlled sputter removal combined with spectroscopy or imaging• Depth distribution from surface and into material (depth resolution < 1nm)• Measurement of film thicknesses and diffusion profiles (< 1 µm thick)
4. 1-3 combined: 3D imaging on submicron scale
TOF-SIMS analysis modes
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Silver, positive ions
x 5
x 50
[amu]100 200 300 500 700 900 1200 1500 1900
3x10
1.0
2.0
3.0
4.0
25 keV Ga+
1011 cm-2Na
K
Ag
Ag2
Ag3
Ag5Ag7 Ag9
Ag11 Ag13 Ag15 Ag17
x5
x50
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K
KŽ
KŽO
H
KŽC
l
K�
ClŽ
K�
Cl�
K‘C
l�
K’C
l‘
K“C
l’
x 5x 500
[amu]50 100 150 200 250 300 350 400 450 500 600 700
5x10
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
Inte
nsity
KClKCL1C_P
KmCl(m-1)
Potassium chloride
K
K2
K2ClK4Cl3
K3Cl2 K6Cl5
K5Cl4
K7Cl6
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Hydroxyapatite, Ca5(PO4)3OH
Ca+
+
Na
Ca
CaO
H
CaŽ
CaP
O
CaŽ
O
CaP
OŽ
CaŽ
OŽ
CaŽ
HO
ŽC
aPO
Ž
CaŽ
PO
�
CaŽ
PO
�
x 20
20 30 40 50 60 80 100 120 140 170
5x10
1.0
2.0
3.0
4.0
Ca
CaO
H
Ca 2
OCa
CaO
H
Ca 2
Ca 2
HO
2
CaP
O
CaP
O2
Ca 2
PO4
Ca 2
PO3
CaP
O3
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Polymer identificationH
CH C
HŽ
CH
�
CŽH
�C
ŽH‘
C�
H�
C�
H‘
C�
H“
C�
H‘
C�
H“
C�
H•
C‘H
“C
‘H•
5 15 25 35 45 55 65 75 85 95
3x10
1.0
2.0
3.0
4.0
5.0
C1Hx
C2Hx C3Hx
C4Hx
C5Hx
CxH2x±1
Polyethylene
CH
CŽH
�
C�
H�
C�
H‘
C�
H�
C�
H‘
C�
H“
C�
H•
C‘H
�
C‘H
“C
‘H•
C’H
‘
C“H
“
15 25 35 45 55 65 75 85 95
3x10
0.5
1.0
1.5
2.0
2.5
3.0C3H3
CH
C7H7
Polystyrene
Jukka Lausmaa, Nordic Polymer Days, Gothenburg, August 17, 2005
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Teflon (PTFE)
C
CF
CFŽ
CF�
C�
FŽ
C�
F�
CŽF
�
CŽF
‘
C�
F‘
C�
F‘
20 30 40 50 60 70 80 90 100 120 140
5x10
0.5
1.0
1.5
C
CF
CF2
CF3
C3F2
C3F3 C2F4
C3F5
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Polystyrene oligomer distribution
x 5
800 1000 1400 1800 2200 2600
4x10
0.2
0.4
0.6
0.8
1.0
1.2
PS 2200 dissolved in chloroform and deposited as monolayer on silver foil
(Irgafos 168 + Ag)+
(antioxidant)
∆m = 104 (styrene repeat unit)
Jukka Lausmaa, Nordic Polymer Days, Gothenburg, August 17, 2005
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Interpretation of oligomer distribution
x 5
800 1000 1400 1800 2200 2600
4x10
0.2
0.4
0.6
0.8
1.0
1.2Analysis of m/z = 1726 peak:1.Assume silver cationized:
Oligomer mass: 1726 – 107 = 16192. How many monomers?
1619 / 104.1 = 15.5615 monomers
3. Mass of endgroups:0.56 * 104.1 = 58 (H + C4H9)
Jukka Lausmaa, Nordic Polymer Days, Gothenburg, August 17, 2005
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23.0
5
43.1
7
107.
02
145.
25 369.
60
493.
56
882.
22
Ion Mass [amu]100 200 300 400 500 600 700 800 900 1000
5x10
0.5
1.0
1.5
2.0
Inte
nsity
Cholesterol on Ag
Ag
(M+Ag)–
(2M+Ag)–
1 mg/ml, 5 yl
Molecular spectra: Cholesterol on silver
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Substance identificationEx: Deprotonated molecular ion, (M-H)-, of cholesterol (C27H45O)
Theoretical spectrum(isotope distribution)
Measured spectrum
• Absolute mass (385.35 u)• Isotope pattern due to 13C
MassC27H45O
386 388 390
Isotope Cluster386 388 390 392
1x10
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
x101
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.073.489%
22.612%
3.503%0.365% 0.029% 0.002% 0.000%
385.
35
386.
34
387.
38/ u
386 388 390 392
2x10
1.0
2.0
3.0
4.0
5.0
Jukka Lausmaa, Nordic Polymer Days, Gothenburg, August 17, 2005
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Spectral features
Elemental targets (e.g. metals):- monoatomic ions (Me+), clusters (Men
+)
Inorganics (e.g., metal oxides, salts, ceramics):- monoatomic ions (Me+), sometimes clusters (Men
+) - oxidized species (MemOn
±)
Polymeric materials:- predominantly molecular fragments- characteristic fragmentation patterns- characteristic fragments
Adsorbates and surface contaminants:- predominantly fragments, often also intact (M+H)+ or (M-H)-
- cationized molecular ions (M + Me)+
- oligomer distributions (M + Me)n+
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Surface analysis:Challenges and questions
• Which elements and compounds are present on the surface?
• Which impurities/contaminants are present?• How are they distributed over the surface?• How are they distributed from the surface and into the
material?• Major challenges:
- Distinguish the surface from the rest of the material- Minute amounts of materials (typically 1-10 ng/cm2)
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te1. Surface spectroscopy (static SIMS):• High surface sensitivity (information depth 1-3 molecular layers)• All elements, incl. isotopes are detected• High mass resolution gives specific chemical information• Low detection limits (% of monolayer down to ppm-ppb)
2. Microscopy (imaging):• Submicron lateral resolution• Analysis of composites, particles, fibres and microfabricated materials• Imaging of lateral distributions at surface or in cross sections
3. Depth profiling (dynamic SIMS):• Controlled sputter removal combined with spectroscopy or imaging• Depth distribution from surface and into material (depth resolution < 1nm)• Measurement of film thicknesses and diffusion profiles (< 1 µm thick)
4. 1-3 combined: 3D imaging on submicron scale
TOF-SIMS analysis modes
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x 10x 100
x 10
x 100
[amu]50 100 150 200 250 300 400 500
5x10
0.5
1.0
1.5
2.0
2.5
y5x10
0.51.01.52.02.53.03.54.0
y
Surface contamination: fingerprint on Al foil
10x
10x
100x
100x
Al foil, as received
Al foil + fingerprint
Mg
Al
C3HyC4Hy
Phthalatefragment
C
CO H+
O
O
Na
AlC2H3
C3Hy
C4Hy
PDM
S (1
47)
PDM
S (2
07)
PDM
S (2
21)
PDM
S (2
81)
∆m=14(CH2)
∆m=14 (fatty acids)
![Page 28: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/28.jpg)
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Identification of surface contamination
x 5
[amu]50 100 150 200 250 300 350 400
5x10
0.5
1.0
1.5
2.0
2.5
3.0 Ti surface handled withPVC gloves
TiO
Ti
Na
phthalatefragment (DEHP+Na)+
(DEHP+H)+
![Page 29: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/29.jpg)
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Examples of common surface contaminants
Type Characteristic peaks
Plasticizers (phthalates) 149, 391 (M+H)+, 413 (M+Na)+
Fatty acids CH3-(CH2)n-COO- 227, 255, 283, ∆m = 28
Synthetic oils ∆m = 140 (C10H20)n
Polydimethyl siloxane 43, 73, 147, 207, 281, ∆m = 74(PDMS)
![Page 30: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/30.jpg)
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Injection moulding of polystyreneCollaboration with Dept Polymeric Materials, Chalmers(Francesco Pisciotti, grad. student)
-Injection moulding widely used processing method-High pressures and high temperatures (<Tm) involved
Objective:Study chemical composition of surfaces and interfaces,especially migration of impurities and additives
![Page 31: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/31.jpg)
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CH
CH
�
CŽH
�
C�
H�
C�
HŽ
C�
H�
C‘H
�
C’H
‘
C“H
“
C”H
“
C•H
“
C�
ŒH
”
C�
�H
•C
�ŽH
” C�
�H
•C
��
H•
C�
�H
�Œ
x 20
[amu]50 100 150 200 250 300 350 400
3x10
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
Injection moulded polystyrene: spectrum from cross section (interior of material)
Characteristic PS spectrum(unsaturated CxHy species dominate) No additives or impuritiesdetected
![Page 32: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/32.jpg)
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CH
�
CŽH
�
C�
H‘
C�
H“
C‘H
•
C’H
•
C“H
“
C•H
“
x 20
[amu]50 100 150 200 250 300 350 400
5x10
0.2
0.4
0.6
0.8
Injection moulded polystyrene: spectrum from surface
Not a characteristic PS spectrum- more saturated CxHy species- traces of CxHyO and CxHyN detected
No specific additives or impuritiesdetected
![Page 33: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/33.jpg)
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x 10
x 200
[amu]200 400 600 800 1200 1600 2000 2400
5x10
0.2
0.4
0.6
0.8
1.0
Ag
Ag2
Ag3
(Irga
nox
1010
+A
g)+
x 200
∆m = 14 (CH2)∆m = 74
Injection moulded polystyrene: extract deposited on Ag-foil
Paraffin wax? PDMS
Jukka Lausmaa, Nordic Polymer Days, Gothenburg, August 17, 2005
![Page 34: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/34.jpg)
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[amu]50 100 150 200 250 350 450 550 650 750
6x10
0.2
0.4
0.6
0.8
1.0
1.2
1.4
AGPRE1P, 04.26.2001, 18:52
x 15
[amu]700 750 800 850 900 950 1000 1100 1200
5x10
0.5
1.0
1.5
Ag
Ag2 Ag
3
(DO
P+A
g)+
X15∆m=140 140 140 140
Ag9
(C10H20)
Injection moulded polystyrene: spectrum from Ag-foil rubbed against surface
Synthetic oil (-C10H20-)n
(314u+Ag)Irgafos 168
Jukka Lausmaa, Nordic Polymer Days, Gothenburg, August 17, 2005
![Page 35: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/35.jpg)
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Separation/purification of biomolecule samplesby liquid chromatography
Mixture ofbiomolecules
Separationcolumn
Y
YY
YY
Y
YY
Surface functionalizedseparation medium
Purifiedsample
![Page 36: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/36.jpg)
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Surface characterization of media for liquid chromatographyCollaboration with Amersham Pharmacia Biotech, Uppsala(Bo-Lennart Andersson and Mikael Andersson)
Background- Function of LC media dependent on morphology and surface
chemistry- Surface modification and ligands chemical specificity- ”Difficult materials”; beads, roughness, non-conducting,
complex chemistry
Objective:- Can ToF-SIMS provide useful information about
surface chemistry?
![Page 37: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/37.jpg)
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Sepharose beads
20 µm
Surface analyst’s nightmare: Insulating + rough and porous + complex chemistry
![Page 38: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/38.jpg)
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Raw materials
O
OHOH
OHO
OO
OHOHHO
*
OO
OHOH
OHO
*n
HOO
OO
OH
OH
O
O
O
HO
D-Galactose 3,6-anhydro-L-Galactose
Dextran (branching exists)Agarose
Alpha-1,6-D-Glucose
Cross-linker
OH
OH
![Page 39: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/39.jpg)
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Comparison of raw materials
Ion Mass [amu]10 20 30 40 50 60 70 80 90 100 110
3x10
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
Inte
nsity
4x10
0.2
0.4
0.6
0.8
Inte
nsity
Agarose
Dextran
C4H5O
C3H5O2
C4H5O2
![Page 40: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/40.jpg)
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Diethyl aminoethyl ligands on cross-linked agarose(DEAE Sepharose Fast Flow)
O NCH2
C2H5
H
CH2 C2H5
![Page 41: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/41.jpg)
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Identification of surface ligands
[amu]20 30 40 50 60 70 80 90 110 130 150
4x10
0.51.01.52.02.53.0
5x10
0.2
0.4
0.6
0.8
1.0
Agarose
Sepharose + DEAE
C2H
5C
H3N
C2H
6N
C3H
6N
C5H12N C6H14N
O NCH2
C2H5
H
CH2 C2H5
![Page 42: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/42.jpg)
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te1. Surface spectroscopy (static SIMS):• High surface sensitivity (information depth 1-3 molecular layers)• All elements, incl. isotopes are detected• High mass resolution gives specific chemical information• Low detection limits (% of monolayer down to ppm-ppb)
2. Microscopy (imaging):• Submicron lateral resolution• Analysis of composites, particles, fibres and microfabricated materials• Imaging of lateral distributions at surface or in cross sections
3. Depth profiling (dynamic SIMS):• Controlled sputter removal combined with spectroscopy or imaging• Depth distribution from surface and into material (depth resolution < 1nm)• Measurement of film thicknesses and diffusion profiles (< 1 µm thick)
4. 1-3 combined: 3D imaging on submicron scale
TOF-SIMS analysis modes
![Page 43: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/43.jpg)
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Chemical imaging
1. Focused ion beam (Au+) is scanned oversurface; spectra from 128 x 128 points
BC
D
10 µm – 10 mm(128 x 128 pxl)
2. Mass spectrum from total area showswhich substances that are present
/ u400 450 500 550 600 650 750 850 950
410
0.2
0.4
0.6
0.8
1.0
1.2
A
D B C
A
A
Results are stored in raw data file, containing>16 000 mass spectra, with retained spatial information.
3. Images are constructed from raw data file, showing where substances are located
A B C D ”Overlay”
(alt: sample stage scan)
signal
![Page 44: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/44.jpg)
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Drying stain on Si wafer
Na2Cl
Na2OH
Al
![Page 45: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/45.jpg)
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Na (contamination)Si (wafer) Ti, W (evaporated)
Impurities on semiconductor devices
Användningsområden:•Processutveckling och kvalitetskontroll•Skadeanalyser
25 µm
![Page 46: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/46.jpg)
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ToF-SIMS imaging: Grain boundary segregationin polycrystalline silicon
20 µm
Si Al K
Ti Al K Ti
Sample from: Dr J. Walmsley, SINTEF Technology, Trondheim, Norway
![Page 47: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/47.jpg)
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Analysis of fatigue crack
Video
Ion images
Ion sputteredarea
Jukka Lausmaa, SP
![Page 48: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/48.jpg)
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Ion imaging of microstamped CH3- and COOH-terminatedthiols on Au (40 and 60 µm stripes)
Au C2H3OC2H3
100 µm
Sample preparation by Department of Polymer Technology, Chalmers
![Page 49: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/49.jpg)
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Paints
• Often complex formulations, containing different additives (antioxidants, UV absorbers, leveling agents, …)
• Car paints; multilayer systems• Interesting questions:
- How are additives distributed?- How do additives diffuse?- Degradation mechanisms?
Need for analysis methods that combine detailed chemicalinformation with imaging capability TOF-SIMS
![Page 50: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/50.jpg)
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Spectrum from surface of car paint
M205 = BHT (additive) – CH3* = silicone (anti foaming agent)
M662 = Irgafos 168 (phosphate)M647 = Irgafos 168 (phosphite)
mass220 240 260 280 300 320 340 360 380
3x10
1.0
2.0
3.0
4.0
5.0
6.0
7.0
Inte
nsity
4x10
1.0
2.0
3.0
4.0
5.0
6.0
Inte
nsity
mass500 600 700 800 900
3x10
0.5
1.0
1.5
Inte
nsity
3x10
1.0
2.0
3.0
4.0
Inte
nsity
Artificially aged, 5000 h
Artificially aged, 5000 h
Unaged
Unaged
205
662647
539
mass10 20 30 40 50 60 70 80 90
5x10
0.5
1.0
1.5
2.0
2.5
3.0
Inte
nsity
5x10
0.5
1.0
1.5
2.0
2.5
Inte
nsity
mass110 120 130 140 150 160 170 180 190
4x10
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
Inte
nsity
4x10
0.2
0.4
0.6
0.8
Inte
nsity
y g
Artificially aged, 5000 h
Artificially aged, 5000 h
Unaged
Unaged
*
*
*
*
*
**
*
*
** *
![Page 51: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/51.jpg)
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Sample preparation for cross section analysis
PMMA Paint
Adhesive
Paint PMMA
Direction of microtomingDirection of microtome
Plastic PlasticPaint Paint
Epoxi
![Page 52: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/52.jpg)
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Imaging of cross sections
Plastic
Layer 1
Layer 2
Layer 3 (topcoat)
Adhesive
![Page 53: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/53.jpg)
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Oxidation of paint system
200 x 200 µm
Sample aged in 18O-enriched air
Analysis:Imaging TOF-SIMS of 18O- ions
Result:Oxidation localized to pigmented layer
Ref: Physical ElectronicsJukka Lausmaa, Nordic Polymer Days, Gothenburg, August 17, 2005
![Page 54: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/54.jpg)
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Chemical mapping of biological samples
Knowledge about molecularcomposition of cells and tissuesimportant for research on:
• understanding diseases• drug development• diagnostic methods
Need for improved analyticalmethods:
• which molecules?• spatial distributions?• relevant length scales; nm – mm
3 nm
Alberts et al.: Molecular Biology of the Cell
Lipid molecule Protein molecule
Lipidbilayer
© Sinauer Associates Inc. ~10 µm
![Page 55: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/55.jpg)
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te• Transfer sample molecules to silver surface with retained lateral distribution
• Imaging TOF-SIMS of chemical imprint
Advantages:+ less fragmentation (Ag cationization) improves identification+ higher SI yield improves sensitivity
Cell imprinting
![Page 56: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/56.jpg)
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Positive TOF-SIMS spectrum of cell imprint
/ u200 400 600 800
5x10
0.5
1.0
1.5
2.0
Inte
nsity
/ u490 500
4x10
0.5
1.0
1.5
2.0
2.5
Inte
nsityph
Ag-ch
Ag-ch2
Ag2 Ag3
Ag2Cl
![Page 57: Material characterization with TOF-SIMSfy.chalmers.se/gsms/TOFSIMS_051208.pdf · Material characterization with TOF-SIMS Part 1: General - secondary ion mass spectrometry - time-of-flight](https://reader031.fdocuments.in/reader031/viewer/2022040723/5e34a42d94b148081d0aabd3/html5/thumbnails/57.jpg)
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Spatially resolved chemical analysis of cells
SEM image of human leukocyte on glass
TOF-SIMS images from imprints on silver
CH4N+ (proteins, DNA) m/z = 184 (phosphocholine)
m/z = 493 (cholesterol + Ag molecular ion)
10 µm
20 µm
P. Sjövall et al. Analytical Chemistry (2003)
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Lipid distributions in mouse brain
cholesterol palmitate (255 u) sulfatide (806-908 u)
cholesterol / palmitat / sulfatid261 u 429 u
P. Sjövall, J. Lausmaa and B. Johansson, Analytical Chemistry,76, 4271-4278, 2004
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te1. Surface spectroscopy (static SIMS):• High surface sensitivity (information depth 1-3 molecular layers)• All elements, incl. isotopes are detected• High mass resolution gives specific chemical information• Low detection limits (% of monolayer down to ppm-ppb)
2. Microscopy (imaging):• Submicron lateral resolution• Analysis of composites, particles, fibres and microfabricated materials• Imaging of lateral distributions at surface or in cross sections
3. Depth profiling (dynamic SIMS):• Controlled sputter removal combined with spectroscopy or imaging• Depth distribution from surface and into material (depth resolution < 1nm)• Measurement of film thicknesses and diffusion profiles (< 1 µm thick)
TOF-SIMS analysis modes
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Depth profiling using ion etching
Ion beam
Sputtertime
Sign
al in
tens
ity
• Layer thicknesses ~1-100 nm• Sputter time vs depth can be calibrated• Depth resolution a few nm
Ion beamMS
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Depth profiling (dynamic SIMS): 28 nm thermal oxide on HF etched titanium
Time (S)200 400 600
110
210
310
410
Substance Mass Color
F 19.00
CH� 15.02
O 15.99
TiO 63.94
Interface
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Applications of depth profiling
• Oxide layers (thickness and composition)• Thin films (optical, conducting, hard coatings, …)• Diffusion profiles• Dopant profiles• …
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Summary
• TOF-SIMS a versatile analysis technique, which combines:- detailed chemical information via high-res. MS- high detection sensitivity- high surface sensitivity- imaging capability at submicron scale
• Important applications:- polymeric materials (additives, molecular weight distr., …)- thin film characterization- cross section analysis- grain boundary segregation - microfabricated materials (e.g., microelectronics, µCP, …)- biological samples (emerging)
However:- Best used in combination with other characterizationtechniques