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Tin Processes for highest Productivity and exceptional throwing power

Research · March 2016

DOI: 10.13140/RG.2.1.4054.4406

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 Tin Processes for highest Productivity and
with exceptional Throwing Power

Olaf Kurtz1, Peter Kühlkamp1, Jürgen Barthelmes1, Robert Rüther1,

Din-Ghee Neoh2, Tan Chee Chow2
1
Atotech Deutschland GmbH
2
Atotech S.E.A. Pte Ltd

Abstract division criteria for matt and bright tin

The Niveostan* range of MSA-based
pure tin processes, have been devel-
oped to combine matt and bright tin
performance benefits whilst fulfilling
the revised classification of tin pro-
cesses by the Tin Whisker User Group
of the International Electronics Manu-
facturing Initiative (iNEMI).
Niveostan* deposits combine morphol-
ogy properties of large crystal grain
size (typical of matt tin) with lowest
roughness (bright tin) and so provide
technical performance beneficial to
whisker risk, discoloration and solder-
ability.
Additional process benefits include
exceptional long term stability at high
current densities in reel-to-reel produc-
tion for Niveostan* 200, whilst Nive-
ostan* A1 provides superior throwing
power properties for rack and barrel
applications.
Both electrolytes will be introduced and
characterized in the following paper.
Introduction
In 2011, the Tin Whisker User Group of
the International Electronics Manufac-
turing Initiative (iNEMI) adopted new
electrodeposits [1].
In accordance with iNEMI criteria, all
tin coatings with grain sizes <1µm are
defined as ‘bright’ and >1µm as ‘matt’.
Since then, technical papers have
been published on a new generation of
matt tin processes (in accordance with
the iNEMI classification [1]), character-
ized by their exceptionally uniform
large grain deposit structure and signif-
icantly reduced roughness, compared
to conventional matt tin processes [2].
By combining these two characteris-
tics, it is possible to minimize whisker
formation and, at the same time, to
improve technical properties, such as
solderability, reflow behavior and wear
resistance/ reduced abrasion during
trim and form processing of lead-
frames.
Electrodeposits from the new Nive-
ostan® SL* combine benefits from both
bright and matt tin processes.
Niveostan® SL* provides a regular
crystal grain size structure that deter-
mines the diffusion behavior, defect
density, intermetallic phase formation/
propagation, and deposit surface
roughness. The latter property has an
immediate effect on wettability or sol-
derability of the tin deposit. Increased
surface roughness (more surface tin
oxide) causes inferior solderability.
Fig.1: SEM image of a FIB cross section of
a Niveostan® SL* tin layer showing regular
large grain sizes with low roughness
The FIB cross section in Figure 1
clearly illustrates the very regular large
2
grain structure of a 20A/dm ,10µm tin
electro-deposit onto copper substrate.
The tin surface is very smooth (an indi-
cation of low roughness) and the grain
boundaries are slightly curved and
primarily perpendicular to the sub-
strate. The very thin, regular interme-
tallic phase developed at the copper
and tin interface shows very little ten-
dency to grow further at the low-energy
grain boundaries.
For the Cu/ Sn system, the dominating
phase is normally the η-Cu 6 Sn 5 phase
[3,4] with a density of 8.27 g/cm3, lower
3
than copper (8.96 g/cm ).
This density reduction causes a vol-
ume expansion and hence increases
the compressive stress within the tin
coating. Latest information suggests
that compressive stress is fundamental
to tin whisker growth. Regular grain
structure, with minimal or an absence
of defects, reduces the grain struc-
ture’s internal compressive stress and
therefore, the probability of whisker
growth. Additionally, low-energy grain
boundaries minimize the diffusion pro-
cess, in particular, the intermetallic
phase along the grain boundaries.
Minimal surface roughness is another
factor for reducing whisker growth,
since the oxide, formed at the tin sur-
face, also influences internal stress
and may impede or completely sup-
press the relaxation process. This can
be demonstrated by removal of the
surface oxide by sputtering, whereby
the system immediately relaxes, result-
ing in a significant drop in the meas-
ured voltage [5]. Conversely, if oxygen
is diffused into the metal coating with
subsequent oxidation of the metal, the
tension within the tin deposit increases
resulting in increased whisker risk [6].
By minimizing all these influencing fac-
tors, whisker risk will generally de-
crease with the increased reliability of
manufactured electronic components
[7].
Expanding this development approach
further, this technical paper describes
two methane sulfonic acid (MSA) –
based, matt tin processes.
2
Niveostan* 200: which has high cur-
rent density stability benefits, ideally
suited for reel-to-reel production.
Niveostan* A1: providing increased
throwing power for rack operation.
Increasing Productivity in Reel-to-
Reel Applications
Niveostan*SL tin process has been
developed for high current density op-
eration with exceptional stability bene-
fits [2], based on increased operation
speed at reduced concentration of tin
and MSA (maintaining the same depo-
sition rate and performance at a cur-
2
rent density of about 25A/ dm ).
In general, MSA and tin MSA contrib-
ute an average of 2/3 of the total costs
of tin plating inventory.
Niveostan* 200 was developed to fur-
ther extend long-term process stability
and also the maximum current density
limit.
Niveostan* 200 electro-deposits have
morphological properties analogous to
those produced from Niveostan* SL.
Study of Morphology and Surface
Roughness
Tin deposit morphology was studied
using a focused ion beam (FIB) in con-
junction with a scanning electron mi-
croscope (SEM). The focused ion
beam (FIB) technique is similar to the
scanning electron microscope (SEM)
but uses ions (usually gallium) instead
of electrons. The SEM exposes the
sample to a fine electron beam and
detects the emitted secondary elec-
trons, depicting a non-destructive sur-
face image. The heavier gallium ions,
used in the FIB technique, sputter the
sample material and enable accurate
cross-sectional and surface structure
imaging to be observed. The precision
of this structure can be compared to
that achieved using the SEM electron
beam and the extremely fine ion beam
required, only became possible from
field ionization development of suitable
ion sources.
FIB can be used as a high-resolution
microscope similar to SEM, with inher-
ent minor sample erosion (even at
lowest possible ion current setting).
This FIB/ SEM combination allows for
accurate positioning of a suitable target
cut area without movement during the
procedure. After the cut has been
made, the region can be examined
using the SEM without disturbing the
sample. Another benefit of this com-
bined technique is the ability to ob-
serve the actual cutting procedure.
The gentle surface erosion by the ion
beam enables the examination of even
the most sensitive structures as an
alternative to invasive classical me-
3
chanical preparation techniques (see
Fig. 2).
Fig. 2: A high-resolution FIB + FE-SEM of
FEI NOVA NANOLAB 600 with a schemat-
ic illustration of the procedure.
Similar to the Niveostan* SL FIB study,
all test samples comprised of 10µm tin
onto copper substrate (C194) prepared
2
at 15 and 25 A/dm , without a nickel
intermediate layer (to enable the as-
sessment of the CuSn phase for-
mation).
Figure 3 presents a detailed view of
the FIB-SEM studies.
Fig.3: FIB-SEM images of C194 samples
plated with 10µm of tin for studying crystal
grain structure and intermetallic phase
formation.
Similar to Niveostan* SL, the Nive-
ostan* 200 crystal structure comprises
very regular large grains with bounda-
ries primarily perpendicular to the sur-
face. The intermetallic phase is also
very regular, very thin and solely de-
veloped at the copper and tin interface,
showing little tendency for growth at
the grain boundaries. No changes in
morphology could be recognized at
either 15 or 25 Adm2.
Roughness was measured using the
relative surface area increase (RSAI)
technique which compares the effec-
tive surface area after tin plating to that
of the initial substrate.
RSAI ‘roughness’ values are normally
measured using an interference micro-
scope (IM, Atos MIC 520) (see Fig. 4)
Fig. 4: interference microscope (Atos MIC
520) and picture of a metallic sample sur-
face.
and calculated from a topographic
comparison of the sample’s three di-
4
mensional surface mapping and its two
dimensional projection (see Fig. 5).
Example: hemispherical structure (radius r) on image 2r x 2r
Three-dimensional area:
4r2- r2+2 r2 =r2(4+ )
Fig.6: Connectors plated with Niveostan*
2 2
r (4+ )-4r
RSAI = 100%
4r2
200 for surface roughness studies.
= 100% /4 = 78.5%

Two-dimensional
Two-dimensional area:
area: Typically for matt tin deposits, RSAI
4r4r2 2
values of approximately 80% are
common compared to only 5% for
Fig. 5: Calculating the RSAI value from bright tin. The lower the RSAI (surface
topographic surface images of the inter-
area increase after plating) value, the
ference microscope
smoother and brighter the coating.
Typical values of 20 % for Niveostan*
100% RSAI reading would infer a dou-
200 were measured, deemed semi-
bling of the surface area.
bright/ matt in nature, and compared to
Test samples consisted of brass con-
those for Niveostan* SL [2].
nector samples plated with 1.25µm
nickel and 2.5µm tin at current densi-
Scanning electron microscope images
ties of 5, 15 and 25 A/dm2. Figure 6
completed the topographical analysis
shows the connector type used and
of the plated test samples (Figure 8)
Figure 7 the topographic images taken
and clearly show the regular grain size
with the interference microscope,
structure and low surface roughness.
thickness and RSAI values.

Fig.7: Roughness measurements with interference microscope to determine RSAI values for
connectors sample versus current density.

5
 The Niveostan* 200 process also ben-
efits from excellent Ah throughput.
Figure 10 depicts the quality of a
Niveostan* 200 tin deposit after
>500kAh (equivalent to 780Ah/lt) reel-

Fig.8: SEM surface images of Niveostan* to-reel throughput.

200 deposit at two varying magnifications.

High Current Densities and Produc-

tivity
The Niveostan SL additive system pro-
vides exceptional stability under high
current density operation [2] with bene-
ficial savings in tin and MSA and also
increasing productivity.
Figure 9 depicts samples plated with
Niveostan SL at which the current den-
sities were calculated from the meas-
ured layer thicknesses and plating
time.

Fig. 10: Tin deposits from a Niveostan*

200 electrolyte after more than 500kAh
(= 780Ah/lt) throughput).

Fig.9: Performance test to check high cur-
rent density stability. Slight burning could
only be observed at the highest current
density (67A/ dm2) [2]
Only at an estimated current density of
2
67 A/ dm could slight burning be ob-
served.
The plated tin deposit above shows a
very homogenous, uniform coloration,
without HCD burning, and exhibiting
excellent throwing power.
After >500kAh (equivalent to 780Ah/lt)
and operated under high current densi-
ty extremes, no loss in technical quality
or ageing of the electrolyte could be
established.

6
Highest Throwing Power Tin Pro- Production Study on Throwing
cess for Rack and Barrel Operation. Power of Tin process.

The following study describes another

tin process from the Niveostan product
range. The MSA-based Niveostan* A1
also benefits from the unique large
crystal grain morphology and low sur-
face roughness. Niveostan* A1 is a
single additive system that can be
easily controlled using UV analysis and
has been designed specifically for rack
Fig. 12: Side view of stacked jig for tin
plating, particularly where high throw-
plating of leadframes.
ing power is required.
Figure 11 presents a plating jig tightly
In this study, the leadframes were plat-
stacked with leadframes. The lead-
ed at 1 A/dm2 for 20 minutes at room
frames are arranged two in each row
temperature with only slight electrolyte
each with a jig total of 16.
agitation and no jig movement.
The experimental matrix (at varying tin
and acid concentration) was used to
compare Niveostan A1 to a conven-
tional matt tin process (table 1).
Variation in deposit thickness was
measured using an X-ray fluorescence
(XRF) technique.
Thickness measurements were taken
Fig. 11: Tightly stacked jig for tin plating of from the 4 leadframes positioned at jig
leadframes.

row 3 where surface shielding was ex-

Figure 12 depicts a side view diagram pected to be greatest (Figure 13).
of the leadframes on the jig.

7
 1 4 7 10 13

2 5 8 11 14

3 6 9 12 15

Fig. 14: Diagram showing leadframe thick-

ness measurement positions.

Figure 15 illustrates graphically the

Fig. 13: Diagram showing leadframes (jig measurements for all leadframes, to-
row 3) where thickness measurements gether with their statistical evaluation.
were taken (highlighted in red). The statistical evaluation program
‘JMP 11.1.1, SAS’ facilitates presenta-
Leg Tin (g/L) Acid (g/L) tion of measurement results in so-
1 15 100 called ‘boxplots’

2 15 150
3 15 200
4 25 100
5 25 150
Tab. 1: Experimental matrix used for plat-
ing of leadframes with Niveostan* A1 at
varying tin and acid concentrations.

For each leadframe, a total of 15 thick-

ness measurement points were taken
(Figure 14).

8
Fig. 15: Leadframe thickness distribution measurement results.

value is less or equal to this specific

50 % of all measurements are located
within the rectangular boxplot. The
boxplot is limited at the lower level by
the first or lower quartile and at the
upper level by the third or upper quar-
tile. Quartile (from Latin) means quar-
ter value. The first quartile presented in
the boxplot signifies that 25 % of data
value. The third quartile accordingly
signifies that 75% of data value is less
or equal to this specific value. Inside
the boxplot is a horizontal bar, called
Median. The Median represents the
data statistical distribution mean value.
Lower and upper “Whisker” or “Anten-
na” represents the measurement data

Fig. 16: Thickness variation summary for jig 3 leadframes for each combination of acid/ tin con-
centration.

9
 outside the boxplot. The whisker or
antenna is calculated from the mini-
mum or maximum data values.
Fig. 17: Average standard deviation study of both electrolyte
ments for all acid/ tin combinations.
Evaluation of thickness measurements
clearly show that, compared to the
conventional matt tin electrolyte, thick-
ness distribution for Niveostan A1 pro-
vides significantly lower throwing pow-
er over the entire measurement range.
The latter, also shows significant dif-
ferences in thickness distribution be-
tween the outer (3-1, 3-4) and inner (3-
2, 3-3) leadframes. As expected, the
inner leadframes provided lower aver-
age thickness than outer-positioned.
The study also demonstrated a de-
crease in throwing power at increasing
acid concentration.
Niveostan* A1, however, provided a
considerably
more
types using stable thickness
all leadframe measure-
distribution with reduced standard vari-
ance over the designated parameter
range, without significant thickness
variation for outer and inner lead-
frames positions, irrespective of acid
concentration.
A slight increase in throwing power
could be observed at higher tin con-
centration and maximum acid concen-
tration limit.
Figure 16 summarizes the variation in
measurements for the selected four
leadframes for each combination of
acid/ tin concentration.
10

An average standard deviation study
was also undertaken to highlight varia-
tions and assist process comparison
(see Figure 17).
(Fig 18, lower leadframe) appear semi-
matt and of a lighter color compared to
conventional electro-deposit (Fig 18,
upper leadframe).

Figure 17 clearly demonstrates the

very reliable thickness distribution
achieved with Niveostan* A1. For the
target 10µm thickness (see Fig. 15), an
average deviation below 2µm for the
Fig. 18: Photo images of conventional matt
lower g/l tin limit increased to
tin (above) and Niveostan A1 electro-
2-3µm for the higher limit.
deposits (bottom).
For the conventional electrolyte, how-
ever, deviations of 3-4.5µm and 4-
Technically, increased surface bright-
5.5µm respectively were observed.
ness corresponds to reduced rough-
A very pronounced standard deviation
ness.
increase was observed at the higher g/l
tin concentrations and a subsequent
As previously described, surface mor-
decrease for the high acid/ low tin con-
phology is observed using a scanning
centration combinations.
electron microscope (SEM) and RSAI
The experimental study also highlight-
(relative surface area increase) values
ed considerable thickness distribution
for Niveostan* 200 deposits have been
and parameter sensitivity for the con-
discussed.
ventional process and in general pro-
vided lower throwing power.
Figures 19 to 21 show leadframe posi-
tion and subsequent SEM surface to-
Morphology Study of Tin Electro-
pography images (40µm section width)
deposits.
for electrodeposits from Niveostan* A1
and conventional matt tin processes at
This technical article has characterized
varying acid level for a 15g/l tin con-
the Niveostan deposits by their signifi-
centration prepared at room tempera-
cantly reduced roughness compared to
ture.
those from conventional matt tin pro-
cesses. Deposits from Niveostan*A1
11
Fig. 19: Top view of SEM image of surface topography at 15g/L tin
and 100g/L acid.

Fig. 20: Top view of SEM image of surface topography at 15g/L tin and
150g/L acid.

Fig. 21: Top view of SEM image of surface topography at 15g/L tin
and 200 g/L acid.

12
All the photo images clearly show in-
creased brightness and whiteness of
the Niveostan* A1 electrodeposit and
the subsequent SEM images highlight
the more homogenous grain size at all
acid concentrations. Calculated RSAI
values conclude this topographical
study and are shown in Figure 22.
RSAI values of only 25-30% were ob-
served for Niveostan* A1 deposits
compared to 50-55 % from a conven-
tional process (the lowest achieved at
15g/l tin/ 150g/l acid).

Fig.22: Calculated RSAI values for tin surfaces of conventional matt tin
electrolyte as well as from Niveostan* A1.

13
Solderability Study from discoloration and corrosion in
Reduced surface roughness (lower humid and warm environments [12-16].
RSAI= also minimizes surface oxide
formation compared to those produced A SnPb alloy was used as solder to
from a conventional process, providing provide a lower soldering temperature.
improved product storage, minimal sur-
Wetting Balance parameters used:
face discoloration and improved sol-
derability or wettability benefits.
Solder SnPb
Solderability/ wettability studies were
Temperature 235 °C
carried out using a suitable ‘Wetting
Immersion time 10 s
balance’ for the ‘as plated’ deposit
Immersion depth 4 mm
condition and also after being subject-
Immersion velocity 20 mm/s
ed to 8 hrs steam aging.
Table 2 shows the test matrix used
This study utilized test pins plated
and includes the benefit of incorporat-
with approx. 10µm tin (20 minutes
ing a post treatment into the plating
at 1 A/dm2) from an electrolyte operat-
sequence.
ed at room temperature with slight so-
lution movement and
Electrolyte Post-Dip
without cathode agi-
Conventional matt tin
1 electrolyte
- After plating tation.

Conventional matt tin

2 electrolyte
- After 8h steam ageing

3 Niveostan A1 - After plating

4 Niveostan A1 - After 8h steam ageing

5 Niveostan A1 Protectostan LF After plating

6 Niveostan A1 Protectostan LF After 8h steam ageing

Table 2: Matrix used for the

solderability study

Protectostan LF* post treatment im-

parts hydrophobic properties to the tin
surface, providing effective protection

14
Figure 23 depicts the wetting balance and ZCT readings, even after 8 hours
profiles for all tests. steam aging.

Fig.23: Wetting curves for studies on solderability at solder balance for both elec-
trolytes before and after 8 h steam aging

Summary
The wetting profiles clearly highlight
This technical paper describes two
the benefit reduced surface roughness
newly developed tin processes from
has on solderability/ wetting perfor-
the Niveostan®* product range.
mance. The wetting of Niveostan* A1
According to iNEMI classification, both
deposits proceed exceptionally fast
are pure matt tin process type, howev-
with a zero crossing time (ZCT) of
er, their exceptional morphology prop-
0.874s (far less than 1.219s for con-
erties, (combining large crystal grain
ventional tin electrodeposits).
size with lowest surface roughness) is
Steam aging greatly accelerates oxide
typical of both matt and bright tin.
formation and the wetting profile for the
Low surface roughness results in re-
conventional tin electrodeposit shows
duced oxide formation and conse-
no surface wetting, whilst wettability
quently provide significant solderability
still occurs for Niveostan* A1 deposits
benefits.
(ZCT of 6.621s).
Comprehensive FIB / SEM studies
Post treatment with Protectostan LF
demonstrated that intermetallic copper/
dramatically highlighted the benefit of
tin phases occur predominantly at the
protection from oxide formation with no
copper substrate/ tin electrodeposit
change to the wetting balance profile

15
interface without any growth tendency
along the low-energy grain boundaries
or as a result of diffusion.
Hence, Niveostan* deposits provide
increased stability of the intermetallic
phase, which is beneficial in minimizing
whisker growth.
The reduced roughness of Niveostan*
electrodeposits significantly reduce the
tendency to discoloration compared to
deposits from conventional matt tin
processes.
Studies also show the Niveostan* 200
process to provide exceptionally high
Ah throughput and excellent stability
when operated under high current
density, reel-to-reel conditions and
providing excellent throwing power,
further improving productivity at mini-
mal chemical cost.
Comprehensive studies of the rack and
barrel Niveostan* A1 process (under
production conditions) using a conven-
tional matt tin benchmark process also
provided exceptional throwing power
benefits from thickness and distribution
measurements.
*® at Atotech Deutschland GmbH
Contact: olaf.kurtz@atotech.com
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