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Surface Analysis … Solving Problems in the PCB Industry

Dr. Alan Brown, CSMA Ltd, Queens Road, Penkhull Stoke-on-Trent ST4 7LQ

Modern surface analysis techniques provide the means of rapidly solving age-old problems
in the PCB industry leading to reduced defect levels.

The complexity of PCB manufacturing has increased dramatically over the last three decades,
progressing from straightforward double-sided boards with 100% through-hole technology to
highly-complex multi-layer PCB’s with mixtures of through-hole, surface mount and chip-on-board
configurations. Board layouts have consequently increased in density with tighter tolerances and
decreased distances between electrical contacts. With this increase in complexity the possibility of
manufacturing defects has also consequently increased. Typical causes of failure include :-
• Board delamination
• Component misalignment
• Broken metal lines
• Cold-solder joints and poor die bonding
• Surface contamination by metal and ionic residues

Industry defect levels are variously reported to be in the range of 100 – 1000 parts per million i.e.
for every million solder joints made, up to 1000 may be faulty. Defects may not “show-up” at the
time of manufacture and return to haunt manufacturers as “field failures” (see later). They can
escape detection by normal in-house test procedures or may not even be included in acceptance
specifications. Nevertheless, defects directly affect the form, fit, function and long-term
performance of PCB’s and for manufacturers, suppliers and customers they represent BAD
NEWS.
Many defects are related to PCB or component surfaces i.e. their chemical and/or physical
composition determines performance. This article describes case studies and examples of where
modern surface analysis techniques (including XPS, Imaging ToFSIMS, Dynamic SIMS and 3DP)
have solved problems for PCB manufacturers and helped to improve their processes.
N.B. It is important to make a distinction between the surface sensitivity of analytical
techniques. XPS and SIMS methods (including ToFSIMS and Dynamic SIMS) take their
information from a depth of only 1 – 5nm. The more routinely-used techniques in industry
e.g. SEM/EDX and FTIR include contributions from the surface but effectively sample
microns in depth. Hence a contaminant which appears only on the surface at a low but
sufficient level to cause problems will be easily detected by XPS/SIMS but may not even
register in SEM/EDX or FTIR analyses.

Case study – Poor solder-wetting of gold contact pads
In this case study the PCB manufacturer was experiencing
problems with non-wetting of solder on gold bond pads. The
problem manifested itself on isolated pad areas where loosely-
attached solder “balls” formed on part of the pad surface instead of
a smooth, continuous solder layer (see image right).
The pads had a conventional layer structure i.e. ~50µm copper /
~8µm nickel / ~0.1µm gold top layer, with the nickel and gold
layers being deposited by a sub-contractor using electroless and immersion processes
respectively. A combination of XPS and SIMS analyses were selected, to identify the cause of

poor wetting and pin-point the
manufacturing step where the problem
occurred. XPS analysis of a typical non-
wetting pad (fig. 1) identifies the
presence of gold, nickel and copper on
the pad surface along with silicon,
carbon, oxygen, nitrogen and chlorine.

Fig.1 XPS spectrum of poor solder-wetting pad area

XPS identified the nickel and copper as oxides. Clearly the detection of nickel and copper is
inconsistent with the as-deposited layer structure. There are only two possible ways that nickel and
copper can be detected by XPS - either through incomplete nickel and gold layer deposition
(unlikely) or by deposition from a contaminated plating bath.

A SIMS depth profile through the gold layer
(fig. 2) confirms that nickel, nickel oxide and
copper species clearly appear on the top gold
surface but decrease markedly beyond a
depth of a few nm - reappearing at the
gold/nickel interface. Hence a contaminated
electroplating bath was isolated as the
probable source of the problem. The presence
of silicon and carbon suggested possible
organic contamination by silicones on the
contact pads.

Fig. 2 DSIMS depth profile of PCB pad from surface , through the
gold layer and beyond the Au / Ni interface.

ToFSIMS analysis , fig. 3,
confirmed the presence of
poly-dimethylsiloxane
(PDMS) residues and

Fig. 3 Part of the ToFSIMS spectrum of a pad area
additional hydrocarbon material.

Imaging ToFSIMS of a PCB pad area (fig. 4) shows the relative distribution of the major
components detected. i.e nickel and copper are concentrated within the pad region whereas PDMS
is distributed over the entire area. The high levels of organic contamination could also be a cause
of poor solder wetting.
Although chemical factors were
suspected as the main reason for
poor solder-wetting, it was
nevertheless prudent to investigate
possible variations in surface
topography of contact pads. For
this, 3DP (3D Non-Contact Profiling
– an optical metrology tool) was
used which measures variations in
surface “height” with nm resolution
over areas from tens of square
microns to hundreds of square
centimetres. Data from bond pad
arrays and an isolated pad are
shown in fig. 5 – no significant pad
to pad variation in topography was
Fig. 4 ToFSIMS images of key species detected in the PCB /
pad area. observed therefore eliminating
physical structure as a contributing
factor to poor wetting.
Alpha = 89° Beta = 14° µm
0 0.5 1 1.5 2 2.5 3 mm µm 0 0.1 0.2 0.3 0.4 mm µm
0 80 0
80
0.2 75
75 0.05 9
0.4 70
70
0.6 65 8
65 0.1
0.8 60
60
1 55 0.15 7
55
1.2 50
50 0.2 6
1.4 45 45

1.6 40 40 0.25 5
35 35
1.8
3 mm 0.3 4
30 30
2
25 25 0.35
2.2 3
20 84 µm
20
2.4
15 15
0.4 2
2.6
10 10
2.8 0.45 1
5
3 mm 5
3 0
0 0.5 0
mm
mm

Fig. 5 3DP views of contact pad array and an isolated pad area showing topography

Based on the surface chemical and physical evidence obtained by XPS, ToFSIMS, DSIMS and
3DP, a contaminated electroplating bath was isolated as the probable source of the poor solder-
wetting problem.

Case study - Field failure due to on-board corrosion

PCB’s are often required to operate in extreme cycles of temperature and humidity, for example in
rail and roadside traffic signalling equipment and telecommunications systems. Although
packaging and encapsulation procedures are designed to stabilise PCB environments, the legacy
of inadequate cleaning procedures during manufacture and board population can store up a range
of on-board defects which will lead to field failures with important consequences. In this case study
a telecommunications system PCB failed several years after continuous operation in a Far East
installation. Testing revealed a clear picture of on-board corrosion with areas between narrow-pitch
SMT IC’s most affected. Other areas of white staining were apparent along with “dendritic” features
on non-populated board areas. XPS and SIMS analysis of these areas revealed consistent levels
of tin and lead from the wave solder process, halides from flux residues and additional ionic
contamination at levels below the detection limit of conventional SEM/EDX analysis. This prompted
a detailed investigation of PCB cleaning procedure effectivity by the manufacturer at all production
stages including sub-contractor supplies. An extract of part of the XPS investigation is shown in the
table below :-

Sample Description C O F Sn Pb N Si Ca Br Mg Cu Cl

PCB as received – No clean 75.3 16.1 4.6 0.9 - 1.1 1.9 - 0.1 - - -

Aqueous clean 72.1 21.5 0.4 2.2 0.3 2.3 1.2 - - - - -

Solvent-based clean 73.8 22.0 - 2.6 0.1 1.1 - - 0.4 - - -

Field failure –corrosion area 51.1 20.7 21.2 0.3 1.0 - - 0.9 - trace 3.7 1.0

The significant finding from the cleaning study was the ubiquitous nature of tin and lead residues.
They were found on all areas of boards, irrespective of manufacturing origin, and persisted after
cleaning with both aqueous and solvent-based treatments.

For the field failure PCB, corrosion areas between IC
contacts were found to contain a complex mixture of
tin, lead and copper oxides, oxyhalides and halides.
This is illustrated in the DSIMS image in fig. 6 where
copper chloride residue (in red) has formed in the
gap between the IC contacts. Tin from the solder
process (in blue) has also accumulated on contacts
and on all areas of the PCB.
The presence of significant levels of solder residues,
tin and lead, along with ionic material on all PCB
areas after production is a latent defect. These
residues are the essential feedstock for corrosion
processes which require heat, humidity and applied
EMF in order to proceed by several possible routes Fig. 6 DSIMS image overlay from a corroded
including redox reactions, galvanic processes, area between IC legs of the field failure PCB,
showing copper chloride (red) and tin (blue).
electrolysis, atmospheric oxidation, ion transport
and ionic salt formation. The long term
consequences of these processes are well known including metal filament and dendrite growth,
potentially leading to contact resistance changes, arcing and complete circuit failure.
On the basis of this analysis, the manufacturer implemented additional inspection tests, a revised
acceptance specification for suppliers and a series of revised in-house cleaning procedures with
consequent product improvements.
In conclusion, modern surface analysis techniques, applied by an experienced team of
scientists, provide a cost-effective way of solving key problems for PCB manufacturers. The
consequent benefits in early detection of defects and optimisation of cleaning treatments
can significantly reduce in-house rejection and long-term field failures.

CSMA Ltd has over 25 years of experience and expertise in trouble shooting and product
development consultancy over the whole manufacturing spectrum including paper, plastics,
medical devices, pharmaceuticals, microelectronics and, of course, PCB technology. For more
information on the company and surface analysis techniques go to www.csma.ltd.uk.