tof-sims analysis of glass fiber cloths for pcb manufacturing · tof-sims analysis of glass fiber...
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PCB Symposium Raleigh 2011
ToF-SIMS analysis of glass fiber clothsfor PCB manufacturing
Dylan Boday1, Michael Haag2, Joe Kuczynski3, Markus Schmidt2, Michael Wahl4, Johannes Windeln2
1 IBM Systems & Technology Group, 9000 S Rita Rd, Tucson AZ 85744-0002, [email protected] IBM Deutschland MBS GmbH, Hechtsheimer Str. 2, D-55131 Mainz, [email protected] IBM Systems & Technology Group, 3605 Hwy 52 N, Rochester MN 55901-1407, [email protected] IFOS GmbH, Trippstadter Straße 120, D-67663 Kaiserslautern, [email protected]
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content
• PCB (Printed Circuit Board) structure
• glass cloth conditioning
• motivation for ToF-SIMS analysis
• analytical setup
• ToF-SIMS results
• summary and outlook
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PCB structure
prepregs
cores
copper lines
heat, pressure
heat, pressure
prepregs: glass fiber cloth pre-impregnated with resin matrix
cores: cured glass cloth/resin composite with structured copper layer(s)
multi-functionality of composite (glass cloth, resin and optional filler)- mechanical properties (strength, CTE...)- dielectric properties (insulation, impedance...)
pictures source: www.lpkf.de
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glass cloth conditioning
glass fibers pre-treated with Silanes for- improved surface wetting (contact angle reduction)- improved matrix adhesion (organofunctional group R to match matrix resin)
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process steps critical with regard to Silanation:- starch size required for yarn processing- pyrolytic de-sizing (thorough?)- Silanation process
source: JPS Composite Materials(wet) application of Silanes
application of starch sizing
pyrolytic de-sizing
glass cloth conditioning
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motivation for ToF-SIMS analysis
CAF: Copper Anodic FilamentThermal cracks:
pictures source: Dynamic Details Inc.
SEM micrograph: IBM
challenges for modern high performance boards- increasing # of copper layers (�40 and above)- decreasing line width and spacing (� 50µm and below)- RoHS (Pb-free solder; solder process + 20K, new resins)
���� known sporadic failures become epidemic!
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motivation for ToF-SIMS analysis
TGA and SEM/EDX results of analysed glass clothindicate presence of undesired material
expected weight loss < 0.1%!
organic debris
TGA analysis and SEM micrographs: IBM
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ToF-SIMS
Time-of-Flight Secondary Ion Mass Spectrometry
(Sample)
extractor accelerates secondary ions to:
mass dispersion via ion flight time:
UqE ⋅=
Uq2
ms
v
st
m
Uq2
m
E2v
⋅
⋅==⇒
⋅
==
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analytical setup
Method: ToF-SIMS static and dynamic mode
Tool: ION-TOF IV at , Germany
Primary ions: 25keV Bi3+ (clusters to promote molecular secondary ions)
Samples: various samples of glass cloth –supposedly de-sized and coated with coupling agent
2116C6
0106C5
2113C4
1080C3
1080B2
2116A1#
clothsuppliersample
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ToF-SIMS - static mode
raw spectra
significant differences especially in the hi-mass region
#6 #6#6
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dynamic mode to distinguish between signals from
surface coverage and bulk material
surface coverage
glass bulk
sputter
removal
sputter
removal
ToF-SIMS - dynamic mode
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ToF-SIMS – first results
� ToF-SIMS imaging capability(microscopic picture 300µmx300µm „in the light of an ion mass“)
� major signals assigned to one of 4 peak groups with commonappearance and behaviour
group A: group B: group C: group D:
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ToF-SIMS – peak groups
group A (glass constituents)
� laterally homogeneous signal
� glass constituents (Li, B, Mg, Al, Si, Ca, Ti, Na, K)
� signal increased after sputter removal of surface layer (≈30nm)� confirms glass constituent
different:
� Na and K: signal increase after sputter on #7,signal decrease on #1 � sizing component?
after sputter removalof surface layer:
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ToF-SIMS – peak groups
group B (inhomogeneity I)
� signal limited to prominent portions of single fibers
� Sulfate component
� signal decreased after sputter removal of surface layer (≈30nm) � confirms surface coverage
residues from sizing or just abrasion debris from plastic bag?
after sputter removalof surface layer:
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ToF-SIMS – peak groups
group C (homogeneous organics)
� laterally homogeneous signal
� mainly hydrocarbons (C7H7, C9H7, C9H9, C10H8)
� phosphate component
� signal decreased after sputter removal of surface layer (≈30nm) � surface coverage
coupling agent?
after sputter removalof surface layer:
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ToF-SIMS – peak groups
group D (inhomogeneity II)
� signal confined to small areas on single fibers
� fragmentation pattern match: Erucamide (m=337)
� signal decreased after sputter removal of surface layer (≈30nm) � surface coverage
coupling agent or residues from sizing?
after sputter removalof surface layer:
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ToF-SIMS – second run
Method: ToF-SIMS static and dynamic mode
Tool: ION-TOF IV at , Germany
Primary ions: 25keV Bi3+ (clusters to promote molecular secondary ions)
Samples: 1. 2116 glass cloth w/ Silane treatment (supplier‘s claim)
- as received- heat cleaned (matching pyrolytic de-sizing)
- UV-ozone cleaned (details undisclosed)
2. pellet of glass raw material (as used to pull fibers for 2116)
analyzed as a reference- as receiced- on freshly fractured surface- on sputter cleaned surface
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first results
NO SiCH3O+ as reported by Norrmann et al (J. Mass Spectrom. 2002, 37, 695-708)
NO other SiC complexes
potentially Silane related: CxHy+ and CxHyO
+
but no change after heat and UV ozone treatment!
Glass cloth
analyses
1,0E+01
1,0E+02
1,0E+03
1,0E+04
1,0E+05
CH
_3
+
C_
2H
_3
+
C_
2H
_5
+
C_
3H
_5
+
C_
3H
_7
+
C_
4H
_7
+
C_
4H
_9
+
C_
5H
_7
+
C_
5H
_9
+
C_
2H
_3
O+
C_
3H
_3
O+
C_
3H
_5
O+
element / fragment
sig
na
l
heat treated
UV ozone
as received
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first results
potentially Silane related species CxHy+ and CxHyO
+
also present on bulk reference sample!
����adsorbates from the ambient
Glass pellet
analyses
1,0E+00
1,0E+02
1,0E+04
1,0E+06
C_
2H
_3
+
C_
2H
_5
+
C_
3H
_5
+
C_
3H
_7
+
C_
4H
_7
+
C_
4H
_9
+
C_
5H
_7
+
C_
5H
_9
+
C_
2H
_3
O+
C_
3H
_3
O+
C_
3H
_5
O+
element/fragment
sig
na
l
fracture surface
sputter cleaned
as received
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summary and outlook
new ToF-SIMS application in reverse engineering:
Silane treatment of glass fibre cloth
first results on supplier samples:
NO Silane related secondary ions detected
� functionalized surface not as desired- Silanes either not present
- or only physisorbed instead of chemisorbed(due to insufficient fibre treatment)
next steps:
�work with supplier to improve Silanation process
�Is “pad cratering” part of the same problem?
�Is this the time to involve „computational materials science“?